CN104704169A - Microfibrous cellulose aggregate, method for manufacturing microfibrous cellulose aggregate, and method for remanufacturing microfibrous cellulose dispersion liquid - Google Patents

Abstract

The fine fibrous cellulose aggregate contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm and a liquid compound containing at least one of water and an organic solvent, and the content of the fine fibrous cellulose is The mass of the whole cellulose aggregate is 6 mass % - 80 mass %, and the content of a liquid compound is 15 mass % or more with respect to the mass of the whole fine fibrous cellulose aggregate.

Description

Fine fibrous cellulose aggregate, method for producing fine fibrous cellulose aggregate, and method for reproducing fine fibrous cellulose dispersion

technical field

The present invention relates to a fine fibrous cellulose aggregate, a method for producing a fine fibrous cellulose aggregate, and a method for reproducing a fine fibrous cellulose dispersion.

This application claims priority based on Japanese Patent Application No. 2012-178345 for which it applied to Japan on August 10, 2012, and Japanese Patent Application No. 2012-178347 for which it applied in Japan on August 10, 2012, and uses the content here.

Background technique

In recent years, materials using reproducible natural fibers have attracted attention due to the substitution of petroleum resources and the improvement of environmental awareness. Among natural fibers, cellulose fibers having a fiber diameter of 10 μm to 50 μm, especially wood-derived cellulose fibers (pulp), have been widely used mainly in the form of paper products.

Further, as cellulose fibers, fine fibrous cellulose having a fiber diameter of nano-order is also known, and applications to various uses have been studied in recent years.

Fine fibrous cellulose is produced, for example, by a method of defibrating pulp after beating (Patent Document 1), or a method of defibrating a cellulose raw material after treating it with a co-oxidant such as N-oxyl and sodium hypochlorite (Patent Document 2).

prior art literature

patent documents

Patent Document 1 Japanese Patent Application Laid-Open No. 2012-036529

Patent Document 2 Japanese Patent Laid-Open No. 2011-184825

Contents of the invention

The problem to be solved by the invention

In the production methods described in Patent Documents 1 and 2, fine fibrous cellulose is obtained in the state of a dispersion (slurry). Therefore, when the factory that manufactures the dispersion liquid of fine fibrous cellulose is separated from the factory that manufactures products using fine fibrous cellulose, the slurry of fine fibrous cellulose is filled in a container and transported.

However, since the dispersion of fine fibrous cellulose is prepared at a low concentration in order to ensure dispersion stability, most of the transported matter is liquid such as water. Therefore, the transportation cost and storage cost per unit of fine fibrous cellulose tend to increase.

An object of one aspect of the present invention is to provide a fine fibrous cellulose aggregate capable of reducing transportation costs and storage costs per unit of fine fibrous cellulose.

In addition, another aspect of the present invention aims to provide a method for producing a fine fibrous cellulose aggregate capable of reducing transportation costs and storage costs per unit of fine fibrous cellulose. Another aspect of the present invention aims to provide a method for reproducing a fine fibrous cellulose dispersion capable of obtaining a fine fibrous cellulose dispersion with reduced transportation and storage costs per unit of fine fibrous cellulose.

solutions to problems

Several aspects of the present invention are shown below.

[1] A fine fibrous cellulose content comprising fine fibrous cellulose with an average fiber width of 2 nm to 50 nm and a liquid compound containing at least one of water and an organic solvent, wherein the fine fibrous cellulose The content is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

[2] The fine fibrous cellulose content according to [1], which further contains an aggregating agent including a salt of a polyvalent metal.

[3] The fine fibrous cellulose content according to [1] or [2], which further contains an acid.

[4] The fine fibrous cellulose content according to [1] or [2], which further contains a base.

[5] The fine fibrous cellulose content according to any one of [1] to [4], wherein 40% by mass or more of the solid content is fine fibrous cellulose.

[6] The fine fibrous cellulose content according to any one of [1] to [5], wherein the fine fibrous cellulose has a maximum fiber width of 50 nm or less.

[7] A method for producing a fine fibrous cellulose content, comprising a concentrating step of concentrating a fine fibrous cellulose dispersion containing fine fibers with an average fiber width of 2 nm to 200 nm. Fibrous cellulose and dispersion medium.

[8] The method for producing fine fibrous cellulose content according to [7], wherein the concentrating step includes an aggregation step and a filtration step, and the aggregation step is to make the fine fibrous cellulose contained in the fine fibrous cellulose dispersion liquid In the step of aggregating fibrous cellulose, the filtering step is a step of filtering the fine fibrous cellulose dispersion after the aggregating step to remove the dispersion medium.

[9] The method for producing fine fibrous cellulose content according to [8], wherein in the aggregation step, an aggregation agent containing a salt of a polyvalent metal is added to the fine fibrous cellulose dispersion to thereby Aggregates fine fibrous cellulose.

[10] The method for producing fine fibrous cellulose content according to [8] or [9], wherein in the case where the surface charge of the fine fibrous cellulose is negative, in the aggregation step, in the fine fibrous cellulose The acid is added to the fibrous cellulose dispersion to aggregate the fine fibrous cellulose.

[11] The method for producing fine fibrous cellulose content according to [8] or [9], wherein when the surface charge of the fine fibrous cellulose is positive, in the aggregation step, the fine fibrous cellulose Alkali is added to the fibrous cellulose dispersion to aggregate fine fibrous cellulose.

[12] The method for producing a fine fibrous cellulose content according to any one of [7] to [11], wherein the fine fibrous cellulose dispersion has a fine fibrous cellulose content of less than 6% by mass .

[13] The method for producing a fine fibrous cellulose content according to [12], wherein, in the concentrating step, concentration is performed so that the content of the fine fibrous cellulose is 6% by mass to 80% by mass.

[14] A method for reproducing a fine fibrous cellulose dispersion, comprising a redispersion step in the fine fibrous cellulose according to any one of [7] to [13] [Method for Producing Content] A dispersion medium is added to the obtained fine fibrous cellulose content to prepare a fine fibrous cellulose containing liquid, and the fine fibrous cellulose containing liquid is subjected to a dispersion treatment.

[15] The method for reproducing a fine fibrous cellulose dispersion according to [14], wherein in the redispersing step, when the surface charge of the fine fibrous cellulose is negative, the fine fibrous cellulose contains The liquid is adjusted to pH 7 or more and pH 12 or less, and when the surface charge of the fine fibrous cellulose is positive, the fine fibrous cellulose-containing liquid is adjusted to be within a pH range of 4 to 7.

[16] One aspect of the present invention is a fine fibrous cellulose aggregate comprising fine fibrous cellulose having an average fiber width of 2 nm to 50 nm and a liquid compound containing at least one of water or an organic solvent, the The content of the fine fibrous cellulose is 6% by mass to 80% by mass relative to the mass of the entire fine fibrous cellulose aggregate, and the content of the liquid compound is 15% by mass relative to the mass of the entire fine fibrous cellulose aggregate above.

[17] One aspect of the present invention may be the fine fibrous cellulose aggregate according to [16], which further contains an aggregation agent containing a salt of a polyvalent metal.

[18] One aspect of the present invention may be the fine fibrous cellulose aggregate according to [16] or [17], which further contains a compound selected from an acid, a cationic surfactant, and a cationic polymer aggregate. At least one of the group consisting of agents.

[19] One aspect of the present invention may be the fine fibrous cellulose aggregate according to [16] or [17], which further contains a compound selected from free alkali, anionic surfactant, and anionic polymer aggregate At least one of the group consisting of agents.

[20] One aspect of the present invention may be the fine fibrous cellulose aggregate according to any one of [17] to [19], which further contains a cellulose plasticizer.

[21] One aspect of the present invention may be the fine fibrous cellulose aggregate according to any one of [17] to [20], wherein the solid contained in the fine fibrous cellulose aggregate 40% by mass or more of the components are the above-mentioned fine fibrous cellulose.

[22] One aspect of the present invention may be the fine fibrous cellulose aggregate according to any one of [16] to [21], wherein the fine fibrous cellulose has a maximum fiber width of 50 nm. the following.

[23] Another aspect of the present invention is a method for producing a fine fibrous cellulose aggregate, which includes a concentrating step of concentrating a first fine fibrous cellulose dispersion containing Fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium.

[24] Another aspect of the present invention may be the method for producing a fine fibrous cellulose aggregate according to [23], wherein the concentrating step includes an aggregating step and a filtering step, and the aggregating step makes the first 1. The fine fibrous cellulose contained in the fine fibrous cellulose dispersion is aggregated, and the filtering step is to filter the first fine fibrous cellulose dispersion after the aggregation step to remove the first dispersed medium.

[25] Another aspect of the present invention may be the method for producing a fine fibrous cellulose aggregate according to [24], wherein in the aggregation step, in the first fine fibrous cellulose dispersion The fine fibrous cellulose is aggregated by adding an aggregation agent containing a polyvalent metal salt.

[26] Another aspect of the present invention may be the method for producing a fine fibrous cellulose aggregate according to [24] or [25], wherein when the surface charge of the fine fibrous cellulose is negative In the aggregating step, at least one selected from the group consisting of acid, cationic surfactant, and cationic polymer aggregating agent is added to the first fine fibrous cellulose dispersion to make the Microfibrous cellulose aggregates.

[27] Another aspect of the present invention may be the method for producing a fine fibrous cellulose aggregate according to [24] or [25], wherein when the surface charge of the fine fibrous cellulose is positive In the aggregating step, at least one selected from the group consisting of alkali, anionic surfactant, and anionic polymer aggregating agent is added to the first fine fibrous cellulose dispersion to make the Microfibrous cellulose aggregates.

[28] Another aspect of the present invention may be the method for producing fine fibrous cellulose aggregates according to any one of [24] to [27], wherein the aggregation step includes plasticizing the cellulose agent is added to the fine fibrous cellulose aggregates.

[29] Another aspect of the present invention may be the method for producing a fine fibrous cellulose aggregate according to any one of [23] to [28], wherein the first fine fibrous cellulose dispersion The content of the fine fibrous cellulose is less than 6% by mass relative to the mass of the entire fine fibrous cellulose aggregate.

[30] Another aspect of the present invention may be the method for producing a fine fibrous cellulose aggregate according to [29], wherein, in the concentrating step, concentration is performed so that the content of the fine fibrous cellulose It is 6 mass % - 80 mass % with respect to the mass of the whole fine fibrous cellulose aggregate.

[31] A method for reproducing a fine fibrous cellulose dispersion, comprising a redispersion step of aggregating the fine fibrous cellulose described in any one of [23] to [30] A second dispersion medium is added to the fine fibrous cellulose aggregate obtained by the method for producing a body, thereby preparing a second fine fibrous cellulose-containing liquid, and dispersing the second fine fibrous cellulose-containing liquid deal with.

[32] The method for reproducing a fine fibrous cellulose dispersion according to [31], wherein in the redispersing step, when the surface charge of the fine fibrous cellulose is negative, the second fine fibrous The fibrous cellulose-containing liquid is adjusted to pH 7 or more and pH 12 or less, and when the surface charge of the fine fibrous cellulose is positive, the second fine fibrous cellulose-containing liquid is adjusted to be within a pH range of 4 to pH 7.

The effect of the invention

According to the fine fibrous cellulose aggregate of one aspect of the present invention, the transportation cost and storage cost per unit of fine fibrous cellulose can be reduced.

When the fine fibrous cellulose aggregate according to one aspect of the present invention contains an aggregation agent or an acid, the redispersibility of the fine fibrous cellulose at the time of redispersing it in a dispersion medium becomes high.

According to the method for producing a fine fibrous cellulose aggregate in another aspect of the present invention, it is possible to produce a fine fibrous cellulose aggregate capable of reducing transportation costs and storage costs per unit of fine fibrous cellulose.

According to the method for reproducing a fine fibrous cellulose dispersion in another aspect of the present invention, it is possible to obtain a fine fibrous cellulose dispersion in which transportation costs and storage costs per unit of fine fibrous cellulose are reduced.

Detailed ways

"Fine fibrous cellulose aggregates"

The fine fibrous cellulose aggregate of the present embodiment contains fine fibrous cellulose and a liquid compound. The fine fibrous cellulose aggregate of the present embodiment has a high concentration of fine fibrous cellulose.

The fine fibrous cellulose aggregate obtained by the production method of this embodiment contains fine fibrous cellulose and a liquid compound, and the fine fibrous cellulose has a high concentration.

The content of the fine fibrous cellulose in the fine fibrous cellulose aggregate is preferably 6% by mass to 80% by mass, more preferably 10% by mass to 50% by mass, and even more preferably 12% by mass to 30% by mass. When the content of the fine fibrous cellulose is less than the aforementioned lower limit, the transportation cost and storage cost per unit of fine fibrous cellulose cannot be reduced. On the other hand, when the content of the fine fibrous cellulose exceeds the aforementioned upper limit, the redispersibility of the fine fibrous cellulose decreases.

Preferably, 40% or more of the solid content contained in the fine fibrous cellulose aggregate is fine fibrous cellulose. Among them, the solid content contained in the fine fibrous cellulose aggregates refers to cellulose and aggregating agent (at least selected from acid, alkali, cationic surfactant, anionic surfactant, cationic polymer aggregating agent, anionic More than one aggregation agent in the polymer aggregation agent). The solid content contained in the fine fibrous cellulose aggregates may contain plasticizers and latex resins in addition to the aforementioned fine fibrous cellulose and aggregation agents.

Furthermore, the fine fibrous cellulose aggregate contains fine fibrous cellulose, a liquid compound, and an aggregating agent, and may contain a plasticizer and latex resin in addition to the aforementioned fine fibrous cellulose, liquid compound, and aggregating agent.

<Fine fibrous cellulose>

Microfibrous cellulose is cellulose fibers or rod-shaped particles with a type I crystal structure that are far narrower and shorter than pulp fibers used in general papermaking applications.

In the diffraction pattern obtained from wide-angle X-ray diffraction photographs, there are characteristic peaks at two positions near 2θ = 14° to 17° and near 2θ = 22° to 23°, from which it can be identified that the fine fibrous cellulose has type I Crystal structure, the wide-angle X-ray diffraction picture using CuKα monochromated by graphite

The crystallinity of the fine fibrous cellulose determined by the X-ray diffraction method is preferably 60% or more, more preferably 65% or more, and still more preferably 70% or more. When the degree of crystallinity is equal to or greater than the aforementioned lower limit, more excellent performance can be expected from the viewpoint of expressing heat resistance and a low linear thermal expansion coefficient. Regarding the degree of crystallinity, an X-ray diffraction pattern can be measured and obtained from the pattern according to a conventional method (Segal et al., Textile Research Journal, Vol. 29, p. 786, 1959).

(fiber width)

The fine fibrous cellulose is cellulose having an average fiber width of 2 nm to 200 nm as determined by observation with an electron microscope. The average fiber width of the fine fibrous cellulose may be 2 nm to 150 nm. The average fiber width of the fine fibrous cellulose is preferably 2 nm to 50 nm, more preferably 2 nm to 30 nm, particularly preferably 2 nm to 15 nm, and most preferably 2 nm to 10 nm. When the average fiber width of the fine fibrous cellulose exceeds the aforementioned upper limit, it is difficult to obtain the characteristics of the fine fibrous cellulose (high strength, high rigidity, high dimensional stability, high dispersibility when compounded with resin, transparency ). When the average fiber width of the fine fibrous cellulose is less than the aforementioned lower limit, the cellulose molecules dissolve in water, making it difficult to obtain the characteristics (high strength, high rigidity, and high dimensional stability) of the fine fibrous cellulose.

The measurement of the average fiber width observed by the electron microscope of the fine fibrous cellulose was performed as follows. A slurry containing fine fibrous cellulose was prepared, and the aforementioned slurry was cast on a grid covered with a carbon film that had been hydrophilized to form a sample for transmission electron microscope (TEM) observation. Scanning electron microscope (SEM) images of the poured surface on glass can also be observed in the case of broad-format fibers. Observation with an electron microscope image is performed at an arbitrary magnification of 1000 times, 5000 times, 10000 times, 20000 times, 50000 times or 100000 times depending on the width of the formed fibers. However, adjustments were made so that the sample, observation conditions, and magnification satisfied the following conditions.

(1) A straight line X is drawn at an arbitrary position in the observation image, and 20 or more fibers intersect the aforementioned straight line X.

(2) A straight line Y perpendicularly intersecting the aforementioned straight line X is drawn in the same image, and 20 or more fibers intersect the aforementioned straight line Y.

For the electron microscope observation image as described above, the widths (short diameters of fibers) of at least 20 fibers each intersecting the straight line X and the fibers intersecting the straight line Y (that is, at least 40 fibers in total) were read. In this way, at least 3 or more sets of electron microscope images as described above are observed, and at least 40 x 3 sets (ie, at least 120) of fiber widths are read. The average fiber width was calculated|required by averaging the fiber width read in this way.

The maximum fiber width of the fine fibrous cellulose is preferably 1000 nm or less, more preferably 250 nm or less, still more preferably 50 nm or less, most preferably 30 nm or less. When the maximum fiber width of the fine fibrous cellulose is not more than the aforementioned upper limit, the strength of the composite material obtained by mixing with the latex resin is high, and the transparency of the composite material is easy to ensure, so it is suitable for transparent applications.

(degree of polymerization)

The degree of polymerization of the fine fibrous cellulose is preferably 50-1500, more preferably 100-1000, still more preferably 150-500. When the degree of polymerization of the fine fibrous cellulose is more than the aforementioned lower limit, more useful fine fibrous cellulose can be obtained, and when it is less than the aforementioned upper limit, when the fine fibrous cellulose aggregates are redispersed in the dispersion medium The redispersibility becomes higher.

The degree of polymerization of fine fibrous cellulose was measured by the following method.

The fine fibrous cellulose (supernatant after centrifugation, concentration: about 0.5% by mass) was spread on a petri dish made of polytetrafluoroethylene, and dried at 60° C. to obtain a dry sheet. The resulting dried sheet was dispersed in a dispersion medium, and the pulp viscosity was measured according to Tappi T230. In addition, a blank test was performed to measure the viscosity using only the aforementioned dispersion medium, and the blank viscosity was measured. The specific viscosity (ηsp) was subtracted by 1 from the value obtained by dividing the pulp viscosity by the blank viscosity, and the intrinsic viscosity ([η]) was calculated using the following formula.

[η]=ηsp/(c(1+0.28×ηsp))

In the formula, c represents the cellulose content at the time of viscosity measurement.

And the degree of polymerization (DP) in this embodiment was computed from the following formula.

DP=1.75×[η]

This degree of polymerization is an average degree of polymerization measured by the viscosity method, and therefore is also called "viscosity average degree of polymerization".

(fiber length)

In the present embodiment, the major axis of the fine fibrous cellulose is defined as the length. The average fiber length of the fine fibrous cellulose is preferably 0.1 μm to 5 μm. When the average fiber length is equal to or greater than the aforementioned lower limit, the strength-improving effect at the time of blending the fine fibrous cellulose into the resin can be sufficiently obtained. When the average fiber length is not more than the above-mentioned upper limit, the mixing property at the time of blending the fine fibrous cellulose into the resin becomes more favorable. The fiber length can be determined by analyzing the electron microscope observation image used for measuring the above-mentioned average fiber width. That is, for the electron microscope observation image as described above, the fiber lengths of at least 20 fibers intersecting the straight line X and at least 20 fibers intersecting the straight line Y (that is, at least 40 fibers in total) are read. In this way, at least 3 or more sets of electron microscope images as described above are observed, and the fiber lengths of at least 40 x 3 sets (that is, at least 120) are read. The fiber lengths thus read were averaged to obtain the average fiber length.

When the fine fibrous cellulose is applied to applications requiring strength such as transparent substrates, the fiber length is preferably slightly longer (specifically, 500 nm to 4 μm), and when it is blended with latex resin, the fiber length is preferably slightly shorter (specifically, 200 nm). ~2μm).

(anionic group, cationic group)

The fine fibrous cellulose may also have anionic groups so that the surface charge becomes negative. The fine fibrous cellulose may also have a cationic group so that the surface charge becomes positive. In addition, the fine fibrous cellulose may have both anionic groups and cationic groups, and in this case, the surface charge of the fine fibrous cellulose may be positive or negative. When the fine fibrous cellulose has both anionic groups and cationic groups, whether the surface charge of the fine fibrous cellulose is positive or negative can be determined according to the respective contents of the anionic groups and cationic groups, and the valences of the anionic and cationic groups. judge. In addition, even when the fine fibrous cellulose has both anionic groups and cationic groups, each content can be measured by the method for measuring the content of anionic groups or cationic groups described later.

When the fine fibrous cellulose has an anionic group or a cationic group, the content thereof is preferably 0.06 mmol/g to 2.0 mmol/g, more preferably 0.1 mmol/g to 1.0 mmol/g, even more preferably 0.2 mmol/g ~0.6mmol/g. When content of a cationic group or anionic group exists in the said range, the hydratability of a fine fibrous cellulose becomes too high, and the viscosity at the time of slurrying becomes low. When the content of anionic groups or cationic groups exceeds the aforementioned upper limit, the hydratability may become too high and the fine fibrous cellulose may dissolve.

As said anionic group, a carboxylic acid group, a phosphoric acid group, a sulfonic acid group etc. are mentioned. Cellulose has a small amount (specifically, 0.1 mmol/g or less) of carboxyl groups even if it is not treated to introduce carboxyl groups.

The content of the anionic group was determined using the method of "Test Method T237cm-08 (2008): Carboxyl Content of pulp" of US TAPPI. In order to be able to measure the content of anionic groups in a wider range, in the used test solution of the aforementioned test method, for dissolving and diluting sodium bicarbonate (NaHCO ₃ )/sodium chloride (NaCl)=0.84g/5.85g to 1000ml of the test solution was carried out in accordance with TAPPI T237cm-08 (2008) except that it was changed to 1.60g of sodium hydroxide so that the concentration of the test solution was actually quadrupled. In addition, in the case of introducing anionic groups, the difference between the measured values of the cellulose fibers before and after the introduction of anionic groups was taken as the actual anionic group content. In addition, in order to avoid deterioration of the cellulose which may occur by heating at the time of heat-drying, the whole dry cellulose fiber obtained by freeze-drying was used as the whole dry cellulose fiber of a measurement sample.

This anion group content measurement method is a measurement method for monovalent anion groups (carboxyl groups), so when the anion group to be quantified is polyvalent, the value obtained as the above-mentioned monovalent anion group content is divided by the number of acid values. Values are taken as anion group content.

The aforementioned cationic group refers to a group having an onium such as ammonium, phosphonium, sulfonium, etc. in the group, and generally has a molecular weight of about 1000 or less. Specific examples include ammonium such as primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium; phosphonium; sulfonium; and groups having these ammonium, phosphonium, or sulfonium.

The group having these ammonium, phosphonium or sulfonium preferably has a group that reacts with the hydroxyl group of cellulose other than ammonium, phosphonium or sulfonium. The group that reacts with the hydroxyl group of cellulose is not particularly limited as long as it reacts with the hydroxyl group to form a covalent bond. For example, an epoxy group or a halohydrin group capable of forming an epoxy group can be mentioned. , active halo, active vinyl, hydroxymethyl, etc. Among them, an epoxy group or a halohydrin group capable of forming an epoxy group is preferable from the viewpoint of reactivity.

Groups having ammonium, phosphonium, or sulfonium can be introduced into cellulose by reacting compounds having these oniums with cellulose. Examples of onium-containing compounds include various glycidyltrialkylammonium halides such as glycidyltrimethylammonium chloride and 3-chloro-2-hydroxypropyltrimethylammonium chloride or their halides. Alcohol type.

The cationic group content is measured by the method described below.

The pulp slurry treated with the cationizing agent was taken as 0.5 g in total dry mass, and diluted with ion-exchanged water to a concentration of 1% by mass (wet weight: 50 g). While fully stirring, 0.67 g of a 30% by mass sodium hydroxide solution was gradually added thereto in small amounts, and the mixture was left to stand for 2 hours. The pulp is filtered, and the pulp on the filter paper is washed with ion-exchanged water. When the pH of the filtrate became 8.5 or less, it was regarded as the end point of washing.

Move the whole amount of pulp on the filter paper to a 100ml screw bottle, in order to measure the water content in the sample, accurately weigh the mass of the pulp at this time and record it. Add 100g of 0.05N hydrochloric acid solution to the accurately weighed pulp, cover the screw bottle, shake vigorously to mix, and let it stand for 1 hour.

Using a well-dried glass filter, filter the slurry in the screw bottle and receive the filtrate in a receiving vessel. Transfer 3 g of the obtained filtrate to a 100 ml beaker, add 2 or 3 drops of methyl red indicator, and titrate with 0.01N sodium hydroxide solution. Continue to add sodium hydroxide solution dropwise, and the color of the solution changes from initial pink to orange and yellow as the end point of titration.

The amount of introduced cationic groups was calculated from the calculation formula shown in Equation 1. It should be noted that the blank value of titration is obtained by titrating 3g of 0.05N hydrochloric acid solution.

[number 1]

V ₀ : blank titration, C _NaOH : concentration of sodium hydroxide solution, W _HCl : amount of hydrochloric acid added to the sample, W ₀ : blank hydrochloric acid collection, V: sample titration, W _sample : sample filtrate collection, W _water : the water content in the sample, W _BD-pulp : the total dry weight of the sample, N: the valence of the substituent

<Liquid Compound>

The liquid compound contained in the fine fibrous cellulose aggregate is a dispersion medium (first dispersion medium) used when producing the fine fibrous cellulose. It is also a dispersion medium (second dispersion medium) used when reproducing fine fibrous cellulose. The liquid compound contained in the fine fibrous cellulose aggregate contains at least one of water or an organic solvent.

As the liquid compound, water alone is preferable from the viewpoint of handling efficiency and cost, but an organic solvent and water may be used in combination, or an organic solvent may be used alone. As the organic solvent, alcohol-based solvents (methanol, ethanol, propanol, butanol, etc.), ketone-based solvents (acetone, methyl ethyl ketone, etc.), ether-based solvents (diethyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, etc.) are preferable. etc.), acetate-based solvents (ethyl acetate, etc.) and other polar solvents.

The content of the liquid compound in the fine fibrous cellulose aggregate is 15% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, based on the mass of the entire fine fibrous cellulose aggregate. When content of a liquid compound is less than the said lower limit, the redispersibility of fine fibrous cellulose may fall.

The content of the liquid compound is preferably 94% by mass or less with respect to the mass of the entire fine fibrous cellulose aggregate.

<Aggregating agent containing polyvalent metal salt>

The fine fibrous cellulose aggregate may contain an aggregating agent including a salt of a polyvalent metal, which is used in the production method of the fine fibrous cellulose aggregate described later.

As specific aggregation agents, aluminum sulfate (aluminum sulfate), polyaluminum chloride, calcium chloride, magnesium chloride, potassium chloride, calcium sulfate, magnesium sulfate, potassium sulfate, lithium phosphate, potassium phosphate, triphosphate Sodium, disodium hydrogen phosphate, etc. One of these aggregating agents may be contained in the fine fibrous cellulose aggregate, or two or more of them may be contained.

Among the aggregating agents containing salts of polyvalent metals, aluminum sulfate is preferable when the surface charge of the fine fibrous cellulose is negative from the viewpoint of aggregation and cost, and the surface charge of the fine fibrous cellulose is positive. In the case of , disodium hydrogen phosphate is preferred.

When the aggregation agent containing a salt of a polyvalent metal is contained in the fine fibrous cellulose aggregate, the content thereof is preferably 0.5 to 300 parts by mass, more preferably 1.0 parts by mass, based on 100 parts by mass of the fine fibrous cellulose - 50 parts by mass, more preferably 2 - 30 parts by mass. When the aggregation agent content is more than the aforementioned lower limit, fine fibrous cellulose aggregates can be obtained in a short time. However, even if the aggregating agent is added in excess of the aforementioned upper limit, the agglomeration hardly improves, and therefore it is useless.

<acid>

When the surface charge of the fine fibrous cellulose is negative (when the fine fibrous cellulose is anionic), the fine fibrous cellulose aggregate may be included in the fine fibrous cellulose aggregate described later. Acids used in the manufacturing process. The acid may be any of inorganic and organic acids.

Sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid etc. are mentioned as an inorganic acid.

Examples of the organic acid include formic acid, acetic acid, citric acid, malic acid, lactic acid, adipic acid, sebacic acid, stearic acid, maleic acid, succinic acid, tartaric acid, fumaric acid, and gluconic acid. One of these acids may be contained in the fine fibrous cellulose aggregate, or two or more of them may be contained.

Among acids, sulfuric acid is preferable from the viewpoint of aggregation and cost.

When the fine fibrous cellulose aggregates contain an acid, the pH thereof is preferably 4.0 or less, more preferably 3.5 or less, and still more preferably 3.2 or less. Here, pH is a value at 23°C.

When the pH of the fine fibrous cellulose aggregate is equal to or less than the aforementioned upper limit, a fine fibrous cellulose aggregate can be obtained in a short time. In addition, when the pH of the fine fibrous cellulose aggregates is not more than the aforementioned upper limit, the redispersibility of the fine fibrous cellulose when the fine fibrous cellulose aggregates are redispersed in a dispersion medium can be improved.

The pH of the fine fibrous cellulose aggregate is preferably 1.0 or higher, more preferably 1.5 or higher, and still more preferably 2.0 or higher. From a practical point of view, it is difficult to set the pH of the fine fibrous cellulose aggregates to be less than the aforementioned lower limit.

<Cationic Surfactant>

When the surface charge of the fine fibrous cellulose is negative (when the fine fibrous cellulose is anionic), the fine fibrous cellulose aggregate may contain a cationic surfactant.

Examples of cationic surfactants include alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, acylamino ethyl diethyl ammonium salts, amido Ethyldiethylamine salt, alkylamidopropyldimethylbenzyl ammonium salt, alkylpyridinium salt, alkylpyridinium sulfate, stearamidomethylpyridinium salt, alkylquinolinium salt, alkyl Quaternary ammonium salts such as isoquinolinium salts, fatty acid polyvinyl polyamides, amidoethylpyridinium salts, acyl cholamide formyl methylpyridinium salts; stearyloxymethylpyridinium salts, fatty acid triethanolamine , fatty acid triethanolamine formate, trioxyethylene fatty acid triethanolamine, hexadecyloxymethylpyridinium salt, p-isooctylphenoxyethoxyethyl dimethylbenzyl ammonium salt, etc. Amine, ether bond quaternary ammonium salt; alkylimidazoline, 1-hydroxyethyl-2-alkylimidazoline, 1-acetamidoethyl-2-alkylimidazoline, 2-alkyl-4-methyl- Heterocyclic amines such as 4-hydroxymethyloxazoline; polyoxyethylene alkylamine, N-alkylpropylenediamine, N-alkylpolyethylenepolyamine, N-alkylpolyethylenepolyamine dimethyl sulfate , alkyl biguanides, long-chain amine oxides and other amine derivatives, etc. One of these cationic surfactants may be contained in the fine fibrous cellulose aggregates, or two or more of them may be contained.

When the fine fibrous cellulose aggregate contains a cationic surfactant, the content thereof is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass, based on 100 parts by mass of the fine fibrous cellulose , and more preferably 2 to 30 parts by mass. When the surfactant content is equal to or greater than the aforementioned lower limit, fine fibrous cellulose aggregates can be obtained in a short period of time. However, even if the surfactant is added in excess of the above-mentioned upper limit value, the agglomeration hardly improves, so it is not beneficial.

<Cationic Polymer Aggregator>

When the surface charge of the fine fibrous cellulose is negative (when the fine fibrous cellulose is anionic), the fine fibrous cellulose aggregate may contain a cationic polymer aggregating agent.

As the type of cationic polymer aggregation agent, acrylamide, dialkylaminoalkyl (meth)acrylate, dialkylaminoalkyl (meth)acrylamide, or their salts or quaternary compounds, etc. Copolymers of cationic monomers, homopolymers or copolymers of these cationic monomers, and the like. One of these cationic polymer aggregation agents may be contained in the fine fibrous cellulose aggregates, or two or more of them may be contained.

When the cationic polymer aggregating agent is contained in the fine fibrous cellulose aggregate, its content is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass, based on 100 parts by mass of the fine fibrous cellulose parts, more preferably 2 to 30 parts by mass. When the content of the polymer aggregating agent is equal to or greater than the aforementioned lower limit, fine fibrous cellulose aggregates can be obtained in a short period of time. However, even if the aggregating agent is added in excess of the aforementioned upper limit, the agglomeration hardly improves, and therefore it is useless.

When the surface charge of the fine fibrous cellulose is negative (when the fine fibrous cellulose is anionic), the fine fibrous cellulose aggregate may contain the above acid, cationic surfactant, cationic polymer at least one of aggregating agents. In addition, in this case, the fine fibrous cellulose aggregate may further contain an aggregation agent containing a salt of a polyvalent metal.

<base>

When the surface charge of the fine fibrous cellulose is positive (when the fine fibrous cellulose is cationic), the fine fibrous cellulose aggregate may contain a base. The base may be an inorganic base compound or an organic base compound.

Examples of inorganic alkali compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, lithium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium carbonate, sodium hydrogencarbonate, calcium carbonate, phosphoric acid Calcium, calcium hydrogen phosphate, etc.

Examples of organic base compounds include ammonia, hydrazine, methylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, diaminoethane, diaminopropane, diaminobutane, diaminobutane, Aminopentane, diaminohexane, cyclohexylamine, aniline, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, Pyridine, N,N-dimethyl-4-aminopyridine, etc.

The above-mentioned base compounds may be used alone or in combination of two or more. Among alkalis, sodium hydroxide is preferable from the viewpoint of aggregation and cost.

When the fine fibrous cellulose aggregates contain alkali, the pH thereof is preferably 10.0 or higher, more preferably 12.0 or higher. Here, pH is a value at 23°C. When the pH of the fine fibrous cellulose aggregate is equal to or higher than the aforementioned upper limit, a fine fibrous cellulose aggregate can be obtained in a short time.

The pH of the fine fibrous cellulose aggregates is preferably 14.0 or less, more preferably 13.0 or less. From a practical point of view, it is difficult to set the pH of the fine fibrous cellulose aggregate to exceed the aforementioned upper limit.

<Anionic surfactant>

When the surface charge of the fine fibrous cellulose is positive (when the fine fibrous cellulose is cationic), the fine fibrous cellulose aggregate may contain an anionic surfactant.

Examples of anionic surfactants include sodium oleate, potassium oleate, sodium laurate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, Sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl allyl ether sulfate, sodium polyoxyethylene dialkyl sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl allyl ether phosphate wait. One type of these anionic surfactants may be contained in the fine fibrous cellulose aggregates, or two or more types may be contained.

When the fine fibrous cellulose aggregate contains an anionic surfactant, the content thereof is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass, based on 100 parts by mass of the fine fibrous cellulose , and more preferably 2 to 30 parts by mass. When the surfactant content is equal to or greater than the aforementioned lower limit, fine fibrous cellulose aggregates can be obtained in a short period of time. However, even if the surfactant is added in excess of the above-mentioned upper limit value, the agglomeration hardly improves, so it is not beneficial.

<Anionic polymer aggregation agent>

When the surface charge of the fine fibrous cellulose is positive (when the fine fibrous cellulose is cationic), the fine fibrous cellulose aggregates may be included in the fine fibrous cellulose content described later. The anionic polymer aggregating agent used in the production method. As the type of anionic polymer aggregation agent, polyacrylic acid, sodium polyacrylate, (meth)acrylic acid or their alkali metal salts and copolymers of (meth)acrylamide; poly(meth)acrylamide Hydrolysis products of acrylamido-2-methylpropyl sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid or their salts and other vinyl sulfonic acids and (meth)acrylic acid or their alkali metal salts and ( Copolymers of meth)acrylamide; carboxymethyl cellulose, carboxymethyl starch, sodium alginate, etc. The fine fibrous cellulose aggregates may contain one or two or more of these anionic polymer aggregation agents.

When the anionic polymer aggregating agent is contained in the fine fibrous cellulose aggregate, the content thereof is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass, based on 100 parts by mass of the fine fibrous cellulose parts, more preferably 2 to 30 parts by mass. When the content of the polymer aggregating agent is equal to or greater than the aforementioned lower limit, fine fibrous cellulose aggregates can be obtained in a short period of time. However, even if the aggregating agent is added in excess of the aforementioned upper limit, the agglomeration hardly improves, and therefore it is useless.

When the surface charge of the fine fibrous cellulose is positive (when the fine fibrous cellulose is cationic), the fine fibrous cellulose aggregate may contain the above-mentioned alkali, anionic surfactant, anionic polymer at least one of aggregating agents. In addition, in this case, the fine fibrous cellulose aggregate may contain an aggregation agent containing a salt of a polyvalent metal.

<plasticizer>

Regardless of the positive or negative of the surface charge of the fine fibrous cellulose, a cellulose plasticizer may be contained in the fine fibrous cellulose aggregate. When the plasticizer is contained in the fine fibrous cellulose aggregates, hydrogen bonding between the fine fibrous celluloses in the concentration step can be suppressed. Therefore, even after increasing the solid content concentration at the time of concentration, dispersion in the redispersion step becomes easy.

Examples of plasticizers include sugars, sugar alcohols, glycerin, ethylene glycol, propylene glycol, butylene glycol, butanediol, cyclobutanediol, butylene glycol, cyclobutanediol, and pentylene glycol. , cyclopentanediol, pentylenetriol, pentaerythritol, cyclopentanetriol, hydroquinone and other polyols; ethylenediamine, trimethylenediamine, triethylenediamine, tetramethylenediamine, Aliphatic amines such as hexamethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; urea-based compounds such as urea. These plasticizers may contain 2 or more types.

When the fine fibrous cellulose aggregate contains a plasticizer, its content is preferably 0.5 to 10,000 parts by mass, more preferably 1.0 to 8,000 parts by mass, based on 100 parts by mass of the fine fibrous cellulose, More preferably, it is 2 mass parts - 5000 mass parts. The redispersibility after concentration of the fine fibrous cellulose aggregates whose plasticizer content is more than the said lower limit value is favorable. However, even if the plasticizer is added in excess of the aforementioned upper limit, the dispersibility is hardly improved, so it is useless.

<Latex resin>

A latex resin may also be contained in the fine fibrous cellulose aggregate. When the latex resin is contained in the fine fibrous cellulose aggregates, it is difficult to form aggregates when the latex resin is mixed with the fine fibrous cellulose dispersion obtained from the fine fibrous cellulose aggregates. Therefore, a composite material of fine fibrous cellulose and latex resin can be easily produced.

Wherein, the latex resin refers to natural resin or synthetic resin particles emulsified in a dispersion medium with a particle size of 0.001 μm to 10 μm. The type of resin constituting the latex resin is not particularly limited, and examples include polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, poly(meth)acrylate Alkyl ester polymers, alkyl (meth)acrylate copolymers, poly(meth)acrylonitrile, polyesters, polyurethanes, polyamides; epoxy resins, oxetane resins, phenolic resins, urea-formaldehyde resins, melamine Precursors of resins, unsaturated polyester resins, silicone resins, diallyl phthalate resins, etc.; and resin emulsions of monomers, oligomers, etc. constituting the aforementioned resins; natural rubber, styrene-butadiene Copolymer, (meth)acrylonitrile-butadiene copolymer, polyisoprene, polychloroprene, styrene-butadiene-methyl methacrylate copolymer, styrene-(meth)acrylic acid Alkyl ester copolymers, etc. In addition, polyethylene, polypropylene, polyurethane, ethylene-vinyl acetate copolymer, or the like emulsified by a post-emulsification method may be used. These latex resins may contain 2 or more types.

<other ingredients>

The fine fibrous cellulose aggregates may contain preservatives, pigments, ultraviolet absorbers, antioxidants and the like as needed.

"Method for producing fine fibrous cellulose aggregates"

The fine fibrous cellulose aggregate is produced by a production method having a concentration step of concentrating a slurry fine fibrous cellulose dispersion containing the fine fibrous cellulose and a liquid compound as a dispersion medium.

<Preparation method of fine fibrous cellulose dispersion>

The fine fibrous cellulose dispersion (the first fine fibrous cellulose dispersion) to be used in the concentration step is made of a fine fibrous cellulose raw material (hereinafter referred to as "cellulose raw material") through a chemical treatment step and a solution. Prepared by the preparation method of the fiber process.

(cellulose raw material)

The cellulose raw material is a raw material containing cellulose, and examples thereof include paper pulp; cotton-based pulps such as cotton linters and lint; non-wood-based pulps such as hemp, straw, and bagasse; fibers separated from sea squirts and seaweeds, etc. Su and so on. Among these, pulp for papermaking is preferable from the viewpoint of easy availability. Examples of pulp for papermaking include hardwood kraft pulp (bleached kraft pulp (LBKP), unbleached kraft pulp (LUKP), oxygen bleached kraft pulp (LOKP), etc.), softwood kraft pulp (bleached kraft pulp (NBKP), Unbleached kraft pulp (NUKP), oxygen bleached kraft pulp (NOKP), etc.), sulfite pulp (SP), sodium carbonate pulp (AP) and other chemical pulp; semi-chemical pulp (SCP), chemical groundwood pulp (CGP) Semi-chemical pulp; groundwood pulp (GP), thermomechanical wood pulp (TMP, BCTMP) and other mechanical pulp; non-wood pulp made of mulberry, yellow daphne, hemp, kenaf, etc.; waste paper as raw material deinked pulp. Among these, kraft pulp, deinked pulp, and sulfite pulp are preferable in terms of availability.

Cellulose raw materials can be used alone or in combination of two or more.

(chemical treatment process)

The chemical treatment step is a step of chemically treating the cellulose raw material. The chemical treatment is at least one of the following steps (a) to (g).

Step (a) is a treatment step using a carboxylic acid compound. The step (b) is a treatment step using an oxyacid containing a phosphorus atom or a salt thereof. Step (c) is a treatment step using ozone. Step (d) is a treatment step using an enzyme. Step (e) is a treatment step using 2,2,6,6-tetramethylpiperidinyloxy radicals (hereinafter referred to as "TEMPO"). Step (f) is a treatment step using sulfuric acid. Step (g) is cationizing agent treatment.

[Treatment with carboxylic acid compounds]

In the treatment with the carboxylic acid compound, the hydroxyl group contained in the cellulose molecule undergoes a dehydration reaction with the carboxylic acid compound to form a polar group (-COO-). Thereby, the bonding force between cellulose fibers becomes weak, and the defibrillation property improves.

Examples of the method of treating the cellulose raw material with a carboxylic acid compound include a method of mixing a vaporized carboxylic acid compound with a cellulose raw material, a method of adding a carboxylic acid compound to a dispersion liquid of a cellulose raw material, and the like. Among them, the method of mixing a gasified carboxylic acid-based compound with a cellulose raw material is preferable because the process is simple and the carboxyl group introduction efficiency becomes high. As a method of gasifying a carboxylic acid compound, the method of heating a carboxylic acid compound is mentioned.

The carboxylic acid-based compound used in this treatment is at least one selected from the group consisting of compounds having two carboxyl groups, acid anhydrides of compounds having two carboxyl groups, and derivatives thereof. Among compounds having two carboxyl groups, compounds having two carboxyl groups (dicarboxylic acid compounds) are preferable.

Examples of compounds having two carboxyl groups include malonic acid (betainic acid, malonic acid), succinic acid (succinic acid, succinic acid), glutaric acid (gum acid, glutaric acid), adipic acid ( acid, adipic acid), 2-methylmalonic acid, 2-methylsuccinic acid, 2-methylglutaric acid, 1,2-cyclohexanedicarboxylic acid, 2-butenedioic acid (maleic acid , fumaric acid), 2-pentenedioic acid, 2,4-hexadenedioic acid, 2-methyl-2-butenedioic acid, 2-methyl-2-pentenedioic acid, 2-methane Methylene succinic acid (itaconic acid), benzene-1,2-dicarboxylic acid (phthalic acid), benzene-1,3-dicarboxylic acid (isophthalic acid), benzene-1,4-dicarboxylic acid Dicarboxylic acid compounds such as carboxylic acid (terephthalic acid) and oxalic acid (oxalic acid).

Examples of acid anhydrides of compounds having two carboxyl groups include maleic anhydride, succinic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, itaconic anhydride, pyromellitic anhydride, 1,2-cyclohexane Acid anhydrides of dicarboxylic acid compounds such as alkane dicarboxylic anhydride or compounds containing multiple carboxyl groups.

As derivatives of acid anhydrides of compounds having two carboxyl groups, at least a part of the hydrogen atoms of the acid anhydrides of compounds having carboxyl groups such as dimethylmaleic anhydride, diethylmaleic anhydride, and diphenylmaleic anhydride are exemplified. Substituent (eg, alkyl, phenyl, etc.) substituted derivatives.

Among them, maleic anhydride, succinic anhydride, and phthalic anhydride are preferred because of their ease of industrial application and ease of gasification.

The mass ratio of the carboxylic acid compound to the cellulose raw material is preferably 0.1 to 500 parts by mass, more preferably 10 to 200 parts by mass, based on 100 parts by mass of the cellulose raw material. When the ratio of a carboxylic acid type compound is more than the said lower limit, the yield of a fine fibrous cellulose can be raised further. However, even if the above-mentioned upper limit is exceeded, the effect of improving the yield does not increase, and the carboxylic acid-based compound is used in vain.

The apparatus used for this treatment is not particularly limited, and for example, a heating reaction vessel with stirring blades, a rotating heating reaction vessel; a pressure vessel with a heating jacket, a rotating pressure vessel; Shaft mixer and twin-shaft mixer; or twin-screw extruder, multi-screw mixing extruder, pressurized kneader, double-wrist kneader and other mixing devices with heating devices.

From the viewpoint of the thermal decomposition temperature of cellulose, the treatment temperature is preferably 250° C. or lower.

Furthermore, when water is contained at the time of processing, it is preferable to set it as 80 degreeC - 200 degreeC, and it is more preferable to set it as 100 degreeC - 170 degreeC.

The treatment time is preferably 10 minutes to 5 hours.

In this treatment, a catalyst can also be used as needed. As the catalyst, basic catalysts such as pyridine, triethylamine, sodium hydroxide, and sodium acetate; and acidic catalysts such as acetic acid, sulfuric acid, and perchloric acid are preferably used.

After the treatment with the carboxylic acid compound, the cellulose dispersion obtained by the treatment is preferably subjected to an alkali treatment of treating with an alkali solution.

The method of alkali treatment is not particularly limited, and for example, a method of immersing treated cellulose in an alkali solution can be mentioned.

The alkali compound contained in the alkali solution may be an inorganic alkali compound or an organic alkali compound. Examples of the inorganic alkali compound include hydroxides of alkali metals or hydroxides of alkaline earth metals, carbonates of alkali metals or carbonates of alkaline earth metals, phosphates of alkali metals or phosphates of alkaline earth metals. Examples of hydroxides of alkali metals include lithium hydroxide, sodium hydroxide, and potassium hydroxide, and examples of hydroxides of alkaline earth metals include calcium hydroxide.

Examples of alkali metal carbonates include lithium carbonate, lithium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium carbonate, and sodium hydrogencarbonate. Calcium carbonate etc. are mentioned as carbonate of an alkaline earth metal.

Examples of the alkali metal phosphate include lithium phosphate, potassium phosphate, trisodium phosphate, and disodium hydrogenphosphate. Calcium phosphate, calcium hydrogen phosphate, etc. are mentioned as phosphate of an alkaline earth metal.

Examples of organic base compounds include ammonia, aliphatic amines, aromatic amines, aliphatic ammonium, aromatic ammonium, heterocyclic compounds, hydroxides thereof, carbonates, and phosphates.

For example, ammonia, hydrazine, methylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, diaminoethane, diaminopropane, diaminobutane, diaminopentane , diaminohexane, cyclohexylamine, aniline, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, pyridine, N , N-dimethyl-4-aminopyridine, ammonium carbonate, ammonium bicarbonate, diammonium hydrogen phosphate, etc.

The above-mentioned base compounds may be used alone or in combination of two or more.

The solvent in the alkaline solution may be any water or an organic solvent, preferably a polar solvent (a polar organic solvent such as water or alcohol), and more preferably an aqueous solvent containing at least water.

In addition, among alkali solutions, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, and ammonia aqueous solution are particularly preferable because of high versatility.

The pH at 25° C. of the alkaline solution in which the cellulose is immersed is preferably 9 or higher, more preferably 10 or higher, and still more preferably 11-14. The yield of fine fibrous cellulose becomes higher that the pH of an alkali solution is more than the said lower limit. However, when the pH exceeds 14, the handleability of the alkaline solution decreases.

[Treatment with Phosphorous Atom-Containing Oxygen Acid or Salt]

In the treatment using an oxyacid containing a phosphorus atom (hereinafter, referred to as "phosphorus oxyacid") or a salt thereof, the hydroxyl group contained in the cellulose molecule and the phosphorus oxyacid having at least (HPO ₄ ) ^2- or its The salt undergoes a dehydration reaction to form a polar group (-O-PO ₃ ^2- ) as shown in the following reaction formula (A). Thereby, the bonding force between the cellulose fibers is weakened, and the defibrillation property is improved.

-OH+HPO ₄ ^2- → -O-PO ₃ ^2- +H ₂ O (A)

Phosphoric acid, metaphosphoric acid, polyphosphoric acid etc. are mentioned as phosphorus oxyacid.

Examples of salts of phosphorus oxyacids include lithium salts, sodium salts, potassium salts, calcium salts, ammonium salts, and organic alkali salts of phosphoric acid, metaphosphoric acid, and polyphosphoric acid.

Phosphorous oxyacids or salts thereof may be used alone or in combination of two or more.

Among the above, phosphoric acid and/or sodium and potassium salts of phosphoric acid are preferred in terms of low cost, ease of handling, and increased efficiency of introducing phosphate groups.

The mass ratio of the phosphorus oxyacid or its salt to the cellulose raw material is, relative to 100 mass parts of the cellulose raw material, the phosphorus oxyacid or its salt is preferably 0.2 mass parts to 500 mass parts in terms of phosphorus element amount, more preferably It is 1 mass part - 400 mass parts, Most preferably, it is 2 mass parts - 200 mass parts. When the ratio of a phosphorus oxyacid or its salt is more than the said lower limit, the yield of a fine fibrous cellulose can be raised further. However, even if the above-mentioned upper limit value is exceeded, the effect of improving the yield does not increase, and the phosphorus oxyacid or its salt is used in vain.

From the viewpoint of the thermal decomposition temperature of cellulose, the heat treatment temperature is preferably 250° C. or lower. In addition, from the viewpoint of suppressing hydrolysis of cellulose, the heat treatment temperature is preferably 100°C to 170°C. Furthermore, when the system to which phosphorus oxyacid or its salt is added during heat treatment contains water, it is preferable to heat at 130° C. or lower, more preferably 110° C. or lower to sufficiently remove and dry the moisture. After that, heat treatment is preferably performed at 100°C to 170°C. In addition, when removing moisture, a reduced-pressure dryer can also be used.

The treatment time is preferably 10 minutes to 5 hours.

After the treatment with a phosphorus oxyacid or a salt thereof, alkali treatment may be performed in the same manner as the treatment with a carboxylic acid compound.

[treatment with ozone]

In the treatment with ozone, some hydroxyl groups of cellulose are replaced by carbonyl groups and carboxyl groups. Thereby, the bonding force between the cellulose fibers is weakened, and the defibrillation property is improved.

Ozone can be generated by supplying an oxygen-containing gas such as air, oxygen, or oxygenated air to a known ozone generator.

Treatment with ozone is performed by exposing the cellulosic raw material to an enclosed space/atmosphere in the presence of ozone.

When the ozone concentration in the ozone-containing gas is 250 g/m ³ or more, there is a risk of explosion, so it must be less than 250 g/m ³ . However, when the concentration is small, the amount of ozone used increases, so it is preferably 50 g/m ³ to 215 g/m ³ . When the ozone concentration is equal to or higher than the aforementioned lower limit, the handling of ozone becomes easier, and the effect of improving the yield of fine fibrous cellulose in the defibrating step becomes higher.

The amount of ozone added to the cellulose raw material is not particularly limited, but is preferably 5 to 30 parts by mass based on 100 parts by mass of the solid content of the cellulose raw material. When the ozone addition amount is more than the said lower limit, the yield improvement effect of the fine fibrous cellulose in a defibrating process becomes higher. However, when it exceeds the said upper limit, the fall of the yield before and behind an ozone process, and the deterioration of dehydration property will arise. In addition, in the defibrating step, the effect of improving the yield of fine fibrous cellulose no longer increases.

The ozone treatment temperature is not particularly limited, and can be appropriately adjusted within the range of 0°C to 50°C. In addition, the ozone treatment time is not particularly limited either, and can be appropriately adjusted within the range of 1 minute to 360 minutes.

It should be noted that after the ozone treatment is performed on the cellulose raw material, additional oxidation treatment may be performed. Chlorine-based compounds such as chlorine dioxide and sodium chlorite can be mentioned as the oxidizing agent used for the additional oxidation treatment.

In addition, after the ozone treatment, the alkali treatment may be performed in the same manner as the treatment with the carboxylic acid compound.

[treatment with enzyme]

In the treatment with enzymes, cellulose can be decomposed using enzymes.

The cellulolytic enzymes used in the enzyme treatment are so-called cellulase enzymes having cellobiohydrolase activity, endoglucanase activity, and β-glucosidase activity.

The cellulolytic enzymes used in the enzyme treatment can be prepared by mixing appropriate amounts of various cellulolytic enzymes and active enzymes, and commercially available cellulase preparations can also be used. Commercially available cellulase preparations have the above-mentioned various cellulase activities, and most of them also have hemicellulase activities.

As commercially available cellulase preparations, there are those derived from Trichoderma, Acremonium, Aspergillus, Phanerochaete, Trametes, Humicola Cellulase preparations of the genus Humicola, Bacillus, etc. Commercially available products of such cellulase preparations are all trade names, for example, Cell leucine T2 (manufactured by HBI), Meicelase (manufactured by Meiji Seika), Novozym188 (manufactured by Novozym), Marti transfected CX10L (produced by Genencor Corporation) and the like.

In the enzyme treatment, hemicellulase-based enzymes may be used alone or in combination as enzymes other than cellulase. Among the hemicellulase-based enzymes, xylanase (xylanase), which belongs to enzymes that decompose xylan, mannanase (mannase), which belongs to enzymes that decompose mannan, and enzymes that belong to enzymes that decompose arabinan, are preferably used. Arabanase (arabanase). In addition, pectinase, which is an enzyme that decomposes pectin, can also be used as a hemicellulase-based enzyme.

The pH of the dispersion during the enzyme treatment is preferably maintained within a range in which the activity of the enzyme used becomes high. For example, in the case of a commercially available enzyme derived from the genus Trichoderma, the pH is preferably between 4 and 8.

In addition, the temperature of the dispersion liquid during the enzyme treatment is preferably kept within a range in which the activity of the enzyme used becomes high. For example, in the case of a commercially available enzyme derived from the genus Trichoderma, the temperature is preferably 40°C to 60°C. When the temperature is lower than the aforementioned lower limit, the enzyme activity decreases and the treatment time becomes longer, and when the temperature exceeds the aforementioned upper limit, the enzyme may be inactivated.

The treatment time of the enzyme treatment is preferably in the range of 10 minutes to 24 hours. When it is less than 10 minutes, the effect of the enzyme treatment is difficult to appear. When the time exceeds 24 hours, the decomposition of the cellulose fibers using the enzyme proceeds excessively, and the average fiber length of the obtained fine fibers may become too short.

In addition, when the enzyme remains in an active state for a predetermined time or longer, the decomposition of cellulose proceeds excessively as described above, and therefore, it is preferable to perform a treatment to stop the enzyme reaction when the predetermined enzyme treatment is completed. As the treatment for stopping the enzyme reaction, for example, the method of washing the enzyme-treated dispersion liquid with water to remove the enzyme, adding sodium hydroxide to the enzyme-treated dispersion liquid so that the pH becomes about 12 to deactivate the enzyme The activation method is a method of inactivating the enzyme by raising the temperature of the dispersion liquid subjected to the enzyme treatment to a temperature of 90°C.

[processing with TEMPO]

In the treatment with TEMPO, an oxidizing agent is reacted with a cellulose raw material in the presence of TEMPO and a halogenated alkali to convert a part of hydroxyl groups of cellulose into carboxyl groups (chemically modify). Thereby, the bonding force between the cellulose fibers is weakened, and the defibrillation property is improved.

The alkali halide used together with TEMPO as an oxidation catalyst is not particularly limited, and alkali iodide, alkali bromide, alkali chloride, alkali fluoride, etc. can be appropriately selected and used.

The oxidizing agent is also not particularly limited, and sodium hypochlorite, sodium chlorite, sodium hypobromite, sodium bromite, and the like can be appropriately selected and used.

The usage-amounts of TEMPO and alkali halides are not particularly limited, but are preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the solid content of the cellulose raw material. When the addition amount of TEMPO and an alkali halide is more than each said lower limit, the yield improvement effect of the fine fibrous cellulose in a defibrating process becomes higher. However, when the above upper limit is exceeded, the effect of improving the yield of fine fibrous cellulose in the defibrating step may no longer increase.

Although the usage-amount of an oxidizing agent is not specifically limited, Preferably it is 1-80 mass parts with respect to 100 mass parts of solid content of a cellulose raw material.

The pH of the dispersion when the dispersion containing the cellulose raw material is treated with TEMPO is appropriately adjusted depending on the type of oxidizing agent used. The pH adjustment of the cellulose raw material dispersion liquid is performed by appropriately adding alkaline substances such as potassium hydroxide and ammonia, or acidic substances such as acetic acid and oxalic acid.

When treating the cellulose raw material with TEMPO, the treatment temperature is preferably in the range of 20° C. to 100° C., and the treatment time is preferably 0.5 hours to 4 hours.

In addition, in order to perform the treatment by TEMPO uniformly, it is preferable to perform the treatment while stirring using various stirring devices.

[treatment with sulfuric acid]

Specifically, the treatment with sulfuric acid is a treatment in which a cellulose raw material is added to an aqueous sulfuric acid solution and heated. Hydrolysis occurs by treating the cellulose with sulfuric acid.

The concentration of the sulfuric acid aqueous solution is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass. When the concentration of the sulfuric acid aqueous solution is more than the above lower limit, the cellulose can be sufficiently decomposed, and when it is not more than the above upper limit, the workability is excellent.

The heating temperature during sulfuric acid treatment is preferably 10°C to 120°C, more preferably 20°C to 80°C. When heating temperature is more than the said lower limit, the decomposition reaction of cellulose can be controlled easily. During heating, in order to prevent the disappearance of water in the sulfuric acid aqueous solution, it is preferable to reflux after condensing the evaporated moisture.

The treatment time is preferably 10 minutes to 5 hours.

[cationizing agent treatment]

For the cationizing agent treatment, a cationizing agent having a quaternary ammonium group and a group reactive with a hydroxyl group of cellulose is used. As specific examples of the cationizing agent, various glycidyl trialkyl ammonium halides such as glycidyl trimethyl ammonium chloride, 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, or Halohydrin type.

By reacting a cationizing agent in the presence of an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, etc.) as a catalyst, cellulose is cationized, and the electric repulsion between cations is enhanced. Thereby, the bonding force between the cellulose fibers is weakened, and the defibrillation property is improved.

Although the usage-amount of a cationization agent is not specifically limited, Preferably it is 10 mass parts - 1000 mass parts with respect to 100 mass parts of solid content of a cellulose raw material. When the usage-amount of a cationization agent is more than the said lower limit, the yield improvement effect of the fine fibrous cellulose in a defibrating process becomes higher. However, when the above upper limit is exceeded, the effect of improving the yield of fine fibrous cellulose in the defibrating step no longer increases.

The treatment temperature in the cationizing agent treatment is preferably in the range of 30° C. to 90° C., and the treatment time is preferably 1 hour to 3 hours.

(Defibration process)

The fibrillating step is a step of microfibrillating and defibrating the cellulose treated in the chemical treatment step in a dispersion medium (liquid compound, first dispersion medium) to obtain a fine fibrous cellulose dispersion containing fine fibrous cellulose .

The cellulose before miniaturization is preferably diluted with a dispersion medium to form a dispersion having a cellulose content of 0.1% by mass to 1.0% by mass relative to the fine fibrous cellulose dispersion. The cellulose content is more preferably 0.2% by mass to 5% by mass relative to the fine fibrous cellulose dispersion, further preferably 0.3% by mass to 3% by mass. When the cellulose content is more than the above lower limit, the defibration efficiency becomes high, and when it is not more than the above upper limit, the increase in viscosity during the defibration process can be prevented.

As a miniaturization method, a method using various pulverization apparatuses may be exemplified. As the pulverizing device, high-speed defibrillator, grinder (stone mortar type pulverizer), high-pressure homogenizer, ultra-high pressure homogenizer, high-pressure impact pulverizer, ball mill, bead mill, disc type refiner can be suitably used , conical refiner, twin-screw mixer, vibration mill, homogeneous mixer under high-speed rotation, ultrasonic disperser, impact crusher, etc. for wet crushing devices, etc. Among them, it is particularly preferable to use a high-pressure homogenizer, a high-speed rotary defibrator, or both.

The fine fibrous cellulose dispersion obtained by the above miniaturization may be directly supplied to the concentration step, or after the fine fibrous cellulose dispersion is centrifuged, the supernatant of the fine fibrous cellulose dispersion may be recovered, and This supernatant is supplied to the concentration process. The fine fibrous cellulose contained in the supernatant tends to have a narrow fiber width.

<Concentration process>

As the concentration method in the concentration step, a method having an aggregation step and a filtration step (hereinafter referred to as "the first concentration method"), a method having a heating step (hereinafter referred to as the "second concentration method"), .). The first concentration method is preferable from the viewpoint of easily obtaining fine fibrous cellulose aggregates with high redispersibility.

From the viewpoint of dispersion stability, the fine fibrous cellulose content of the fine fibrous cellulose dispersion supplied to the concentration step is preferably less than 6% by mass, more preferably 3.0% by mass or less, based on the fine fibrous cellulose dispersion. From the viewpoint of the productivity of the fine fibrous cellulose aggregates, the fine fibrous cellulose content of the fine fibrous cellulose dispersion supplied to the concentration step is preferably 0.2% by mass or more relative to the fine fibrous cellulose dispersion, more preferably Preferably it is 0.5 mass % or more.

In addition, in the concentration step, it is preferable to set the content of the fine fibrous cellulose in the obtained fine fibrous cellulose aggregate to 6% by mass to 80% by mass relative to the fine fibrous cellulose dispersion, more preferably to set It is 10 mass % - 50 mass %, More preferably, it is 12 mass % - 30 mass %. When the content of the concentrated fine fibrous cellulose relative to the fine fibrous cellulose dispersion liquid is set to be more than the aforementioned lower limit, transportation costs and storage costs can be further reduced, and when it is less than the aforementioned upper limit, it can be easily And it can produce fine fibrous cellulose aggregates in a short time.

(the first enrichment method)

The 1st concentration method is a method including the method which has an aggregation process and a filtration process. The aggregating step in the first concentration method is a step of aggregating the fine fibrous cellulose contained in the fine fibrous cellulose dispersion.

As a method of aggregating fine fibrous cellulose, when the surface charge of the fine fibrous cellulose is negative, adding an aggregating agent containing a salt of a polyvalent metal, a cationic A method of at least one of a surfactant, a cationic polymer aggregation agent, and an acid. When the surface charge of the fine fibrous cellulose is positive, for example, adding an aggregation agent containing a salt of a polyvalent metal, an anionic surfactant, or an anionic polymer aggregation agent to the fine fibrous cellulose dispersion and at least one of bases.

Examples of specific aggregating agents containing polyvalent metal salts to be added to the fine fibrous cellulose dispersion include aluminum sulfate (aluminum sulfate), polyaluminum chloride, calcium chloride, magnesium chloride, and potassium chloride. , calcium sulfate, magnesium sulfate, potassium sulfate, lithium phosphate, potassium phosphate, trisodium phosphate, disodium hydrogen phosphate, etc. One of these aggregating agents may be contained in the fine fibrous cellulose aggregate, or two or more of them may be contained.

Among the aggregation agents, aluminum sulfate is preferable when the surface charge of the fine fibrous cellulose is negative, and hydrogen phosphate is preferable when the surface charge of the fine fibrous cellulose is positive from the viewpoint of aggregation and cost. Disodium.

In the case of adding an aggregation agent containing a salt of a polyvalent metal, the amount added is preferably 0.5 parts by mass to 300 parts by mass, more preferably 1.0 parts by mass to 50 parts by mass, and furthermore Preferably it is 2 to 30 parts by mass. When the addition amount of the aggregating agent is more than the above lower limit, the fine fibrous cellulose can be easily aggregated. However, even if it is added in excess of the aforementioned upper limit, the aggregation property is hardly improved, so it is not beneficial.

Examples of cationic surfactants to be added to the fine fibrous cellulose dispersion include alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, acyl Aminoethyldiethylammonium salt, amidoethyldiethylamine salt, alkylamidopropyldimethylbenzyl ammonium salt, alkylpyridinium salt, alkylpyridinium sulfate, stearamidomethylpyridinium Salt, alkyl quinolinium salt, alkyl isoquinolinium salt, fatty acid polyvinyl polyamide, amidoethylpyridinium salt, acyl cholamide formyl methyl pyridinium salt and other quaternary ammonium salts; stearyl oxide methylpyridinium salt, fatty acid triethanolamine, fatty acid triethanolamine formate, trioxyethylene fatty acid triethanolamine, hexadecyloxymethylpyridinium salt, p-isooctylphenoxyethoxyethyl Ester bond amine such as dimethyl benzyl ammonium salt, ether bond quaternary ammonium salt; alkyl imidazoline, 1-hydroxyethyl-2-alkyl imidazoline, 1-acetamidoethyl-2-alkyl imidazoline, Heterocyclic amines such as 2-alkyl-4-methyl-4-hydroxymethyloxazoline; polyoxyethylene alkylamine, N-alkylpropylenediamine, N-alkylpolyethylenepolyamine, N-alkane Amine derivatives such as polyvinyl polyamine dimethyl sulfate, alkyl biguanide, long-chain amine oxide, etc.

One of these cationic surfactants may be contained in the fine fibrous cellulose aggregates, or two or more of them may be contained.

Examples of the cationic polymer aggregating agent added to the fine fibrous cellulose dispersion include acrylamide, dialkylaminoalkyl (meth)acrylate, dialkylaminoalkyl (meth)acrylic Copolymers of cationic monomers such as amides or their salts or quaternary compounds, or homopolymers or copolymers of these cationic monomers. One of these cationic polymer aggregation agents may be contained in the fine fibrous cellulose aggregates, or two or more of them may be contained.

When adding a cationic surfactant or a cationic polymer aggregating agent, the amount added is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass, based on 100 parts by mass of the fine fibrous cellulose parts, more preferably 2 to 30 parts by mass. A fine fibrous cellulose dispersion having a surfactant content equal to or greater than the aforementioned lower limit can easily aggregate fine fibrous cellulose, shorten filtration time, and obtain a fine fibrous cellulose-containing liquid in a short time. However, even if it is added in excess of the aforementioned upper limit, the aggregation property is hardly improved, so it is not beneficial.

The acid to be added to the fine fibrous cellulose dispersion may be any inorganic acid or organic acid. Sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid etc. are mentioned as an inorganic acid. Examples of the organic acid include formic acid, acetic acid, citric acid, malic acid, lactic acid, adipic acid, sebacic acid, stearic acid, maleic acid, succinic acid, tartaric acid, fumaric acid, and gluconic acid. One of these acids may be contained in the fine fibrous cellulose aggregate, or two or more of them may be contained.

Among acids, sulfuric acid is preferable from the viewpoint of aggregation and cost.

When adding an acid, the pH of the obtained fine fibrous cellulose aggregate is preferably set to 4.0 or less, more preferably 3.0 or less. Adding an acid so that the pH becomes not more than the aforementioned upper limit value facilitates the accumulation of negatively charged fine fibrous cellulose, thereby shortening the filtration time and obtaining a fine fibrous cellulose-containing liquid in a short time. However, when the amount of acid added is small and the pH exceeds the aforementioned upper limit, the negatively charged fine fibrous cellulose aggregates weakly, making it difficult to remove the dispersion medium during filtration in the next step.

The pH of the fine fibrous cellulose aggregate is preferably set to 1.0 or higher, more preferably 1.5 or higher. From a practical point of view, it is difficult to set the pH of the fine fibrous cellulose aggregates to be less than the aforementioned lower limit.

In addition, an acid may be added to the fine fibrous cellulose dispersion together with the above-mentioned aggregating agent containing a salt of a polyvalent metal, a cationic surfactant, and a cationic polymer.

Examples of the anionic surfactant to be added to the fine fibrous cellulose dispersion include sodium oleate, potassium oleate, sodium laurate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, Sodium Dialkyl Sulfosuccinate, Sodium Polyoxyethylene Alkyl Ether Sulfate, Sodium Polyoxyethylene Alkyl Allyl Ether Sulfate, Sodium Polyoxyethylene Dialkyl Sulfate, Polyoxyethylene Alkyl Ether Phosphate, Polyoxyethylene Vinyl alkyl allyl ether phosphate, etc.

The fine fibrous cellulose aggregates may contain one of these anionic surfactants, or may contain two or more of them.

Examples of the anionic polymer aggregating agent added to the fine fibrous cellulose dispersion include copolymerization of polyacrylic acid, sodium polyacrylate, (meth)acrylic acid or their alkali metal salts with (meth)acrylamide Hydrolyzed products of poly(meth)acrylamide, acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, vinylsulfonic acid or their salts and other vinylsulfonic acids and (meth)acrylic acid Or their copolymers of alkali metal salts and (meth)acrylamide, carboxymethyl cellulose, carboxymethyl starch, sodium alginate, etc. One type of these anionic polymer aggregation agents may be contained in the fine fibrous cellulose aggregates, or two or more types may be contained.

When an anionic surfactant or an anionic polymer aggregating agent is added, the amount added is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass, based on 100 parts by mass of the fine fibrous cellulose parts, more preferably 2 to 30 parts by mass. A fine fibrous cellulose dispersion having a polymer aggregation agent content of not less than the lower limit can easily aggregate fine fibrous cellulose, shorten filtration time, and obtain a fine fibrous cellulose-containing liquid in a short time. However, even if it is added in excess of the aforementioned upper limit, the aggregation property is hardly improved, so it is not beneficial.

The base added to the fine fibrous cellulose dispersion may be an inorganic base compound or an organic base compound.

Examples of inorganic alkali compounds include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, lithium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium carbonate, sodium hydrogencarbonate, calcium carbonate, phosphoric acid Calcium, calcium hydrogen phosphate, etc.

Examples of organic base compounds include ammonia, hydrazine, methylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, diaminoethane, diaminopropane, diaminobutane, diaminobutane, Aminopentane, diaminohexane, cyclohexylamine, aniline, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, Pyridine, N,N-dimethyl-4-aminopyridine, etc.

The above-mentioned base compounds may be used alone or in combination of two or more. Among alkalis, sodium hydroxide is preferable from the viewpoint of aggregation and cost.

When adding an alkali, the pH of the fine fibrous cellulose aggregates is preferably set to 10.0 or higher, more preferably 12.0 or higher. When a base is added so that the pH becomes equal to or higher than the aforementioned lower limit value, the positively charged fine fibrous cellulose can be easily aggregated, the filtration time can be shortened, and the fine fibrous cellulose-containing liquid can be obtained in a short time. However, when the added amount of alkali is small and the pH is lower than the aforementioned lower limit, the positively charged fine fibrous cellulose aggregates weakly, making it difficult to remove the dispersion medium during filtration in the next step.

The pH of the fine fibrous cellulose aggregates is preferably set to 14.0 or less, more preferably 13.0 or less. From a practical point of view, it is difficult to set the pH of the fine fibrous cellulose aggregate to exceed the aforementioned upper limit.

In addition, a base may be added to the fine fibrous cellulose dispersion liquid together with the above-mentioned aggregating agent containing a polyvalent metal salt, an anionic surfactant, and an anionic polymer aggregating agent.

In the case of adding a cellulose plasticizer, examples of the plasticizer to be added to the microfibrous cellulose dispersion include sugar, sugar alcohol, glycerin, ethylene glycol, propylene glycol, butylene glycol, Butanetriol, cyclobutanediol, butanediol, cyclobutanediol, pentylene glycol, cyclopentanediol, pentylenetriol, pentaerythritol, cyclopentanetriol, hydroquinone and other polyols; Amine, trimethylenediamine, triethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and other aliphatic Amines; urea compounds such as urea. These plasticizers may contain 2 or more types.

When adding a plasticizer, its content is preferably 0.5 to 10,000 parts by mass relative to 100 parts by mass of the fine fibrous cellulose, more preferably 1.0 to 8,000 parts by mass, and even more preferably 2 to 5,000 parts by mass. parts by mass. The redispersibility after concentration of the fibrous cellulose dispersion liquid whose additive content is more than the said lower limit value is favorable. However, even if it is added in excess of the aforementioned upper limit, the dispersibility at the time of redispersion hardly improves, so it is useless.

When the surface charge of the fine fibrous cellulose is negative, the plasticizer of the cellulose may be mixed with at least one of the above-mentioned aggregating agents containing polyvalent metal salts, acids, cationic surfactants, and cationic polymer aggregating agents. One is added together to the fine fibrous cellulose dispersion. When the surface charge of the fine fibrous cellulose is positive, the cellulose plasticizer may be mixed with at least one of the above-mentioned aggregation agents containing polyvalent metal salts, alkalis, anionic surfactants, and anionic polymer aggregation agents. One is added together to the microfibrous cellulose dispersion.

The filtration step in the first concentration method is a step of filtering the fine fibrous cellulose dispersion after the aggregation step to remove the dispersion medium. It is not necessary to completely remove the dispersion medium, and it is sufficient to remove a part of the dispersion medium.

As a filtration method in a filtration process, the well-known filtration method using filter media, such as a filter paper, a filter cloth, and a resin filter, can be applied.

The pore size of the filter medium is preferably 100 nm to 3000 nm, more preferably 200 nm to 1000 nm, from the viewpoint of the separability of the dispersion medium and the filtration time.

(the second concentration method)

The heating step in the second concentration method is a step of heating the fine fibrous cellulose dispersion to volatilize and remove the dispersion medium.

As the heating method, a method of filling a container with a fine fibrous cellulose dispersion with an open top and heating the container, heating a launder with an open top and flowing a fine fibrous cellulose dispersion in the launder method, the method of directly heating the microfibrous cellulose dispersion, etc.

The heating temperature is preferably set to 40°C to 120°C, and more preferably set to 60°C to 105°C. When the heating temperature is set above the lower limit, the dispersion medium can be quickly volatilized, and when it is below the upper limit, the cost required for heating and the thermal decomposition of cellulose can be suppressed.

"Method for reproducing fine fibrous cellulose dispersion"

The fine fibrous cellulose dispersion (second fine fibrous cellulose dispersion) can be reproduced using the fine fibrous cellulose aggregates.

That is, the method for reproducing a fine fibrous cellulose dispersion includes a redispersion step of adding a dispersion medium (second dispersion medium) to a fine fibrous cellulose aggregate to prepare a fine fibrous cellulose-containing liquid , and the above-mentioned fine fibrous cellulose-containing liquid is subjected to a dispersion treatment.

In other words, the remanufacturing of a fine fibrous cellulose dispersion refers to a method for producing a fine fibrous cellulose dispersion having a redispersion step comprising preparing a fine fibrous cellulose dispersion by adding a dispersion medium to the above fine fibrous cellulose aggregates. A step of fine fibrous cellulose containing liquid, and a step of dispersing fine fibrous cellulose in the fine fibrous cellulose containing liquid.

As the dispersion medium added to the fine fibrous cellulose aggregate in the step of preparing the fine fibrous cellulose-containing liquid, the same dispersion medium as the liquid compound contained in the fine fibrous cellulose aggregate can be used. However, the dispersion medium does not have to be the same as the liquid compound.

In the step of preparing the fine fibrous cellulose-containing liquid in the redispersion step, it is preferable to set the fine fibrous cellulose content of the fine fibrous cellulose-containing liquid to 0.1% by mass to 10% by mass relative to the fine fibrous cellulose-containing liquid. % by mass is more preferably set to 0.2% by mass to 3% by mass. When the fine fibrous cellulose content of the fine fibrous cellulose-containing liquid is more than the aforementioned lower limit, the dispersion stability of the fine fibrous cellulose becomes high, and when it is less than the aforementioned upper limit, the viscosity of the fine fibrous cellulose becomes low. It will become too high, and the operation becomes easier.

The fine fibrous cellulose content of the fine fibrous cellulose-containing liquid can be adjusted according to the addition amount of the dispersion medium, and the greater the addition amount of the dispersion medium, the lower the fine fibrous cellulose content.

In addition, since the redispersibility becomes higher in the redispersion step, when the surface charge of the fine fibrous cellulose is negative, it is preferable to add an alkali to the fine fibrous cellulose-containing liquid. When the surface charge of the fine fibrous cellulose is positive, it is preferable to add an acid.

The alkali added in the redispersion step is the same alkali as the alkali used in the alkali treatment in the above-mentioned concentration step. In addition, the acid is the same as the acid used in the said concentration process also about an acid.

In addition, you may add an acid or alkali to a fine fibrous cellulose containing liquid, stirring a fine fibrous cellulose containing liquid.

When the surface charge of the fine fibrous cellulose is negative, it is preferable to set the pH (23° C.) of the liquid containing the fine fibrous cellulose to 7 or more and 12 or less, more preferably, by adding an alkali. 9 or more and 12 or less, more preferably 11 or more and 12 or less. When the pH of the fine fibrous cellulose dispersion is set to be more than the above lower limit, the redispersibility of the fine fibrous cellulose becomes higher.

When the surface charge of the fine fibrous cellulose is positive, it is preferable to set the pH (23° C.) of the fine fibrous cellulose-containing liquid within a range of 4 to 7 by adding an acid. Within the above range, the redispersibility of the fine fibrous cellulose becomes higher.

As the dispersing device used for the dispersing treatment, for example, the same device as the pulverizing device used in the above-mentioned defibrating step can be used. One type of crushing device may be used alone, or two or more types may be used in combination. When using two or more of the aforementioned dispersing devices in combination, they may be used one by one in sequence or may be used simultaneously.

Even for a fine fibrous cellulose-containing liquid having a high content of fine fibrous cellulose, it is preferable to use an ultrasonic disperser as a dispersing device from the viewpoint of being able to easily redisperse the fine fibrous cellulose.

In the step of dispersing the fine fibrous cellulose in the redispersing step, it is preferable to set the fine fibrous cellulose content of the fine fibrous cellulose dispersion to 0.1% by mass to 10% by mass relative to the fine fibrous cellulose dispersion. %, more preferably set to 0.2% by mass to 3% by mass. When the fine fibrous cellulose content of the fine fibrous cellulose dispersion is more than the above-mentioned lower limit, the dispersion stability of the fine fibrous cellulose becomes high, and when it is below the above-mentioned upper limit, the viscosity of the fine fibrous cellulose becomes low. will become too high, and the operation becomes easier.

The fine fibrous cellulose content of the fine fibrous cellulose dispersion can be adjusted according to the added amount of the dispersion medium, and the more the added amount of the dispersion medium, the lower the fine fibrous cellulose content.

In the above-mentioned remanufacturing method, it is preferable to select the dispersion treatment conditions, alkali or acid addition conditions so that the average fiber width B of the fine fibrous cellulose contained in the remanufactured fine fibrous cellulose dispersion liquid is the same as that supplied to the above-mentioned The ratio (B/A) of the average fiber width A of the fine fibrous cellulose contained in the fine fibrous cellulose dispersion in the concentration step is 0.5 to 2.0, more preferably 0.5 to 1.0. If B/A is within the aforementioned range, the average fiber width of the fine fibrous cellulose contained in the remanufactured fine fibrous cellulose dispersion is different from the average fiber width of the fine fibrous cellulose contained in the fine fibrous cellulose dispersion subjected to the concentration step. The fiber width of the cellulose is substantially equal or becomes narrower. Therefore, the fine fibrous cellulose contained in the remanufactured fine fibrous cellulose dispersion liquid is easy to obtain the characteristics (high strength, high rigidity, high dimensional stability, and stability when compounded with resin) as the original fine fibrous cellulose. High dispersion, transparency).

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, an acid, and a cellulose plasticizer, The content of the fine fibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of the present embodiment contains fine fibrous cellulose having an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, an inorganic acid, and a cellulose plasticizer , the content of the fine fibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of the present embodiment contains fine fibrous cellulose having an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, a cationic surfactant, and cellulose. As for the plasticizer, the content of the fine fibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, a dialkyldimethylammonium salt, and As a plasticizer for cellulose, the content of the fine fibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of the present embodiment contains fine fibrous cellulose having an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, a cationic polymer aggregating agent, and cellulose The content of the plasticizer in the microfibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, an aggregation agent containing a salt of a polyvalent metal, A plasticizer for acid and cellulose, the content of the fine fibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, an aggregation agent containing a salt of a polyvalent metal, Inorganic acid and cellulose plasticizer, the content of fine fibrous cellulose is 6% by mass to 80% by mass, and the content of liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, aluminum sulfate, an acid, and a cellulose extender. As for the plasticizer, the content of the fine fibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, an aggregation agent containing a salt of a polyvalent metal, For cationic surfactants and cellulose plasticizers, the content of fine fibrous cellulose is 6% by mass to 80% by mass, and the content of liquid compounds is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, an aggregation agent containing a salt of a polyvalent metal, Dialkyldimethylammonium salt and plasticizer of cellulose, the content of fine fibrous cellulose is 6% by mass to 80% by mass, and the content of liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, aluminum sulfate, a cationic surfactant, and As a plasticizer for cellulose, the content of the fine fibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, an aggregation agent containing a salt of a polyvalent metal, For the cationic polymer aggregating agent and the plasticizer for cellulose, the content of fine fibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, aluminum sulfate, a cationic polymer aggregation agent, As well as the cellulose plasticizer, the content of the fine fibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, an alkali, and a cellulose plasticizer, The content of the fine fibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, an inorganic alkali compound, and a plasticizer of the cellulose. The content of the fine fibrous cellulose is 6 mass % to 80 mass %, and the content of the liquid compound is 15 mass % or more.

The fine fibrous cellulose aggregate of the present embodiment contains fine fibrous cellulose having an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, an anionic surfactant, and cellulose. As for the plasticizer, the content of the fine fibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of the present embodiment contains fine fibrous cellulose having an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, an anionic polymer aggregation agent, and cellulose The content of the plasticizer in the microfibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, an aggregation agent containing a salt of a polyvalent metal, Alkali and cellulose plasticizer, the content of fine fibrous cellulose is 6% by mass to 80% by mass, and the content of liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, an aggregation agent containing a salt of a polyvalent metal, For the inorganic alkali compound and the plasticizer for cellulose, the content of the fine fibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of the present embodiment contains fine fibrous cellulose having an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, disodium hydrogen phosphate, alkali, and cellulose The content of the plasticizer in the microfibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, an aggregation agent containing a salt of a polyvalent metal, For anionic surfactants and cellulose plasticizers, the content of fine fibrous cellulose is 6% by mass to 80% by mass, and the content of liquid compounds is 15% by mass or more.

The fine fibrous cellulose aggregate of the present embodiment contains fine fibrous cellulose having an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, disodium hydrogen phosphate, and an anionic surfactant. , and a plasticizer for cellulose, the content of the fine fibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, an aggregation agent containing a salt of a polyvalent metal, Anionic polymer aggregating agent and cellulose plasticizer, the content of fine fibrous cellulose is 6% by mass to 80% by mass, and the content of liquid compound is 15% by mass or more.

The fine fibrous cellulose aggregate of this embodiment contains fine fibrous cellulose with an average fiber width of 2 nm to 50 nm, a liquid compound containing at least one of water and an organic solvent, disodium hydrogen phosphate, and an anionic polymer aggregate. An agent and a plasticizer for cellulose, the content of the fine fibrous cellulose is 6% by mass to 80% by mass, and the content of the liquid compound is 15% by mass or more.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The salt aggregating agent and the acid aggregating agent aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The aggregating agent of salt and the aggregating agent of inorganic acid aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step. In the aggregation step, adding aluminum sulfate and acid to the first fine fibrous cellulose dispersion. The aggregating agent aggregates the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The aggregating agent of salt and the aggregating agent of cationic surfactant aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The salt aggregating agent and the dialkyldimethylammonium salt aggregating agent aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, aluminum sulfate and cationic cellulose are added to the first fine fibrous cellulose dispersion. The aggregating agent of the surfactant aggregates the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The aggregating agent of the salt and the aggregating agent of the cationic polymer aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, aluminum sulfate and cationic cellulose are added to the first fine fibrous cellulose dispersion. The aggregating agent of the polymer aggregating agent aggregates the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The salt aggregating agent and the alkali aggregating agent aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The aggregating agent of salt and the aggregating agent of inorganic alkali compound aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of filtering the first fine fibrous cellulose dispersion after the aggregation step to remove the first dispersion medium. In the aggregation step, adding disodium hydrogen phosphate and The alkaline aggregating agent aggregates the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The aggregating agent of salt and the aggregating agent of anionic surfactant aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of filtering the first fine fibrous cellulose dispersion after the aggregation step to remove the first dispersion medium. In the aggregation step, adding disodium hydrogen phosphate and The aggregating agent of anionic surfactant aggregates the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The aggregating agent of the salt and the aggregating agent of the anionic polymer aggregating agent aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of filtering the first fine fibrous cellulose dispersion after the aggregation step to remove the first dispersion medium. In the aggregation step, adding disodium hydrogen phosphate and The aggregating agent of the anionic polymer aggregating agent aggregates the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of filtering the first fine fibrous cellulose dispersion after the aggregation step to remove the first dispersion medium. In the aggregation step, adding acid and cellulose containing The aggregating agent of the plasticizer aggregates the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of filtering the first fine fibrous cellulose dispersion after the aggregation step to remove the first dispersion medium, wherein in the aggregation step, adding an inorganic acid and cellulose Aggregating agent of the plasticizer to aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, in which a cationic surfactant is added to the first fine fibrous cellulose dispersion in the aggregation step Aggregating agent and plasticizer of cellulose to aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the agglomeration step, wherein in the agglomeration step, adding dialkyldimethylformamide to the first fine fibrous cellulose dispersion Aggregating agent of ammonium salt and cellulose plasticizer to aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of filtering the first fine fibrous cellulose dispersion after the aggregation step to remove the first dispersion medium. In the aggregation step, adding a cationic polymer aggregate containing Aggregating agent and plasticizer of cellulose to aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The aggregating agent of salt, acid, and cellulose plasticizer aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The aggregating agent of salt, inorganic acid, and cellulose plasticizer aggregates the fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of filtering the first fine fibrous cellulose dispersion after the agglomeration step to remove the first dispersion medium. In the agglomeration step, adding aluminum sulfate, acid, And an aggregating agent of a plasticizer of cellulose to aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The aggregating agent of salt, cationic surfactant, and cellulose plasticizer aggregates the fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The aggregating agent of salt, dialkyldimethylammonium salt, and cellulose plasticizer aggregates the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of filtering the first fine fibrous cellulose dispersion after the aggregation step to remove the first dispersion medium. In the aggregation step, adding aluminum sulfate, cationic Aggregating agent of surfactant and plasticizer of cellulose to aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The aggregating agent of salt, the aggregating agent of cationic polymer, and the aggregating agent of plasticizer of cellulose aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of filtering the first fine fibrous cellulose dispersion after the aggregation step to remove the first dispersion medium. In the aggregation step, adding aluminum sulfate, cationic The polymer aggregation agent and the aggregation agent of the cellulose plasticizer aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of filtering the first fine fibrous cellulose dispersion after the aggregation step to remove the first dispersion medium. In the aggregation step, adding an alkali and cellulose to the first fine fiber dispersion The aggregating agent of the plasticizer aggregates the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the agglomeration step, wherein in the agglomeration step, adding an inorganic alkali compound and fiber The aggregating agent of the plasticizer of the element is used to aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of filtering the first fine fibrous cellulose dispersion after the aggregation step to remove the first dispersion medium. In the aggregation step, adding an anionic surfactant to the first fine fibrous cellulose dispersion Aggregating agent and plasticizer of cellulose to aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of filtering the first fine fibrous cellulose dispersion after the aggregation step to remove the first dispersion medium. In the aggregation step, adding an anionic polymer aggregate to the first fine fibrous cellulose dispersion Aggregating agent and plasticizer of cellulose to aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The aggregating agent of salt, alkali, and plasticizer of cellulose aggregates the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The aggregating agent of the salt, the inorganic alkali compound, and the plasticizer of the cellulose aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of filtering the first fine fibrous cellulose dispersion after the aggregation step to remove the first dispersion medium. In the aggregation step, adding disodium hydrogen phosphate, disodium hydrogen phosphate, Alkali, and an aggregating agent of a plasticizer of cellulose to aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The aggregating agent of salt, anionic surfactant, and cellulose plasticizer aggregates the fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of filtering the first fine fibrous cellulose dispersion after the aggregation step to remove the first dispersion medium. In the aggregation step, adding disodium hydrogen phosphate, disodium hydrogen phosphate, An anionic surfactant and an aggregating agent of a cellulose plasticizer to aggregate the fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of removing the first dispersion medium by filtering the first fine fibrous cellulose dispersion after the aggregation step, wherein in the aggregation step, a polyvalent metal-containing The aggregating agent of salt, an anionic polymer aggregating agent, and the aggregating agent of cellulose plasticizer aggregate the aforementioned fine fibrous cellulose.

The method for producing fine fibrous cellulose aggregates according to the present embodiment includes a concentrating step of first fine fibrous cellulose containing fine fibrous cellulose having an average fiber width of 2 nm to 200 nm and a first dispersion medium. A step of concentrating the dispersion, the concentration step having an aggregation step and a filtration step, the aggregation step is a step of aggregating the fine fibrous cellulose contained in the first fine fibrous cellulose dispersion, the filtering step is A step of filtering the first fine fibrous cellulose dispersion after the aggregation step to remove the first dispersion medium. In the aggregation step, adding disodium hydrogen phosphate, disodium hydrogen phosphate, An anionic polymer aggregating agent and an aggregating agent of a cellulose plasticizer to aggregate the fine fibrous cellulose.

Example

<Example 1-1> (chemical treatment process)

As a cellulose raw material, a hardwood bleached kraft pulp (LBKP) having a carboxyl group content of 0.06 mmol/g, a solid content concentration of 30% by mass (moisture content of 70% by mass), and a total dry mass of 20 g was prepared. Put the above LBKP in a container, introduce 30L of ozone-oxygen mixed gas with an ozone concentration of 200g/ ^m3 into the container, and shake it at 25°C for 2 minutes. The ozone addition rate at this time was 30 mass % with respect to pulp dry mass. After standing still for 6 hours, the ozone and air in the container were removed to complete the ozone oxidation treatment. After the treatment, the suspension was washed with ion-exchanged water, and the washing was repeated until the pH of the washing water became 6 or more. Then, it filtered under reduced pressure using filter paper, and obtained the ozonated pulp whose solid content density|concentration was 20 mass %.

Next, add 200 g (relative to the total dry mass of the cellulose fiber, equivalent to 3% by mass of sodium chlorite) of an aqueous solution of sodium chlorite to 100 g (20 g by total dry mass) of the ozonated pulp, and heat the pulp at 70° C. The reaction was carried out for 3 hours, and an additional oxidation treatment was performed. The aqueous sodium chlorite solution was a 0.3% by mass sodium chlorite aqueous solution whose pH was adjusted to 4 to 5 with hydrochloric acid. After the additional oxidation treatment was completed, suspension washing was performed with ion-exchanged water, and the washing was repeated until the pH of the washing water became 6 or higher, thereby obtaining oxidation-treated pulp.

Ion-exchanged water was added to the oxidized pulp (20 g by total dry mass) to prepare a dispersion liquid having a solid content concentration of 2% by mass. Sodium hydroxide was added to this dispersion so that the concentration of sodium hydroxide would become 0.3% by mass, and after stirring for 5 minutes, it was left still at room temperature for 30 minutes. After the treatment, suspension washing was performed with ion-exchanged water, and the washing was repeated until the pH of the washing water became 8 or less, thereby obtaining a dispersion liquid containing alkali-treated pulp.

(Defibration process)

Next, ion-exchanged water was added to the dispersion containing the alkali-treated pulp to prepare an aqueous cellulose fiber dispersion having a cellulose fiber concentration of 0.5% by mass. Using a defibrating treatment device (manufactured by MTechnique Co., Ltd, Creamix-2.2S) under the condition of 21,500 rpm, the aforementioned cellulose fiber aqueous dispersion was subjected to a defibrating treatment for 30 minutes to obtain fine fibrous cellulose dispersion. liquid.

The resulting microfibrous cellulose dispersion was subjected to centrifugation at 12,000 G x 10 minutes (centrifuge: manufactured by Kokusan Co., Ltd., "H-200NR"), and the supernatant was recovered, and ions were added to the supernatant Water was exchanged to obtain a supernatant (A) having a cellulose content of 0.2% by mass.

(gathering process)

While stirring 110.5 g of the supernatant (A), 4 N sulfuric acid aqueous solution (mineral acid) was added to aggregate fine fibrous cellulose to obtain a gel-like aggregate at pH 2.8.

(filtering process)

A PTFE membrane filter (ADVANTEC company, pore size 0.5 μm) pre-soaked in isopropanol was placed on a Buchner funnel-type glass filter (manufactured by Advantech Co., Ltd., KG-90) with a sintered size of 30 μm to 50 μm, And set it on the filter bottle. The filtration area at this time was 0.00441 m ² .

Next, the obtained gel-like aggregates were placed on the aforementioned membrane filter at 23° C. under atmospheric pressure, and suction filtration was performed using an aspirator (suction pressure: 0.08 MPa) to concentrate the gel-like aggregates to obtain fine particles. Fibrous cellulose aggregates.

(redispersion process)

The fine fibrous cellulose aggregates obtained in the filtration step were added to water to obtain a fine fibrous cellulose-containing liquid. While stirring the fine fibrous cellulose-containing liquid, 1N sodium hydroxide was added to adjust the pH to 11.6. The total mass at this time was set to 110.5 g, which was the same as the supernatant (A) before the aggregation step. Thereafter, using a homomixer (manufactured by IKA, ULTRA-TURRAX), redispersion treatment was performed for 1 minute under the condition of 11,000 revolutions/minute, thereby obtaining a fine fibrous cellulose aqueous dispersion.

<Example 1-2>

Except not having added sodium hydroxide to the fine fibrous cellulose-containing liquid in the redispersion step, it carried out similarly to Example 1-1, and obtained the fine fibrous cellulose aqueous dispersion liquid.

<Example 1-3>

Except for omitting the aggregation step in Example 1-1 and concentrating the supernatant (A) instead of the gel-like aggregates in the filtration step, it was carried out in the same manner as in Example 1-1 to obtain fine fibrous cellulose water Dispersions.

<Example 2-1> (chemical treatment process)

1.69 g of sodium dihydrogenphosphate dihydrate and 1.21 g of disodium hydrogenphosphate were dissolved in 3.39 g of water to obtain an aqueous solution of a phosphoric acid compound (hereinafter, referred to as "phosphorylation reagent"). The pH of the phosphorylation reagent was 6.0 at 25°C.

The same LBKP as that used in Example 1 was diluted with ion-exchanged water so that the water content became 80% by mass, thereby obtaining a cellulose raw material dispersion. Add 6.29 g (with respect to 100 mass parts of dried pulp, 20 mass parts in terms of phosphorus element amount) of the aforementioned phosphorylation reagent to 15 g of this cellulose raw material dispersion liquid, while using a 105 ° C blow dryer (Yamato Scientific Co. , Ltd.DKM400) Knead every 15 minutes while drying until the quality becomes constant. Next, heat treatment was performed with a blow dryer at 150° C. for 1 hour to introduce phosphoric acid groups into the cellulose.

Next, 300 ml of ion-exchanged water was added to the phosphoric acid group-introduced cellulose, washed while stirring, and then dehydrated. The dehydrated pulp was diluted with 300ml of ion-exchanged water, and while stirring, 5ml of 1N aqueous sodium hydroxide solution was gradually added in small amounts to obtain an alkali-treated pulp dispersion with a pH of 12 to 13. Thereafter, the alkali-treated pulp dispersion was dehydrated and washed by adding 300 ml of ion-exchanged water. This dehydration/washing was repeated twice more.

(Defibration process)

Ion-exchanged water was added to the pulp after washing and dehydration, followed by stirring to prepare a 0.5% by mass dispersion. Using a defibrating treatment device (manufactured by M Technique Co., Ltd., Creamix-2.2S), under the condition of 21500 rpm, the dispersion was subjected to a defibrating treatment for 30 minutes to obtain a fine fibrous cellulose dispersion.

The resulting microfibrous cellulose dispersion was subjected to centrifugation at 12,000 G x 10 minutes (centrifuge: manufactured by Kokusan Co., Ltd., "H-200NR"), and the supernatant was recovered, and ions were added to the supernatant Water was exchanged to obtain a supernatant (B) having a cellulose content of 0.2% by mass.

(gathering process)

While stirring 110.5 g of the supernatant (B), 4N sulfuric acid aqueous solution (mineral acid) was added to aggregate fine fibrous cellulose to obtain a gel-like aggregate at pH 1.5.

(Filtration process · Redispersion process)

The filtration step and the redispersion step in Example 1-1 were carried out in the same manner to obtain a fine fibrous cellulose aqueous dispersion.

<Example 2-2>

Except not having added sodium hydroxide to the fine fibrous cellulose-containing liquid in the redispersion step, it carried out similarly to Example 2-1, and obtained the fine fibrous cellulose aqueous dispersion liquid.

<Example 2-3>

Except for omitting the aggregation step in Example 2-1 and concentrating the supernatant (B) instead of the gel-like aggregates in the filtration step, it was carried out in the same manner as in Example 2-1 to obtain fine fibrous cellulose water Dispersions.

<Example 3-1> (chemical treatment process and defibrillation process)

Using the same LBKP as that used in Example 1-1, beating was performed for 200 minutes with a Niagara beater (capacity 23 liters, manufactured by Tozai Seiki Co., Ltd.) to obtain a cellulose raw material dispersion (pulp concentration: 2% by mass) .

The cellulose raw material dispersion was dehydrated so that the concentration became 3% by mass, the pH was adjusted to 6 with 0.1% by mass of sulfuric acid, and after heating to 50°C in a water bath, 3% by mass of enzyme was added to the pulp (in terms of solid content) Optimase CX7L (manufactured by Genencor) was reacted at 50° C. for 1 hour while stirring to perform enzyme treatment. Thereafter, the enzyme was heated at 95° C. or higher for 20 minutes to inactivate the enzyme, thereby obtaining an enzyme-treated dispersion liquid.

While washing the enzyme-treated dispersion with ion-exchanged water, it was filtered under reduced pressure (using No. 2 filter paper, ADVANTEC Co.) until the conductivity at a cellulose content of 1% by mass became below the specified value (10 μS/cm). The residue on the filter paper was put into ion-exchanged water and stirred to prepare a 0.5% by mass dispersion. The dispersion liquid was subjected to micronization treatment (defibration) at 21,500 rotations for 30 minutes using a high-speed rotary defibrator ("Creamix" manufactured by M Technique Co., Ltd.) to obtain a fine fibrous cellulose dispersion liquid.

The obtained fine fibrous cellulose dispersion was centrifuged in the same manner as in Example 1-1, and the concentration was adjusted to obtain a supernatant (C).

(aggregation process · filtration process · redispersion process)

Using the supernatant (C), the steps of aggregation, filtration, and redispersion in Example 1-1 were carried out in the same manner to obtain a fine fibrous cellulose aqueous dispersion.

<Example 3-2>

Except not having added sodium hydroxide to the fine fibrous cellulose-containing liquid in the redispersion step, it carried out similarly to Example 3-1, and obtained the fine fibrous cellulose aqueous dispersion liquid.

<Example 3-3>

Except for omitting the aggregation step in Example 3-1 and concentrating the supernatant (C) instead of the gel-like aggregates in the filtration step, it was carried out in the same manner as in Example 3-1 to obtain fine fibrous cellulose water Dispersions.

<Example 4-1> (chemical treatment process and defibrillation process)

The same LBKP as that used in Example 1-1 was dried at 105° C. for 3 hours to obtain a dried pulp having a water content of 3% by mass or less. Next, 4 g of dry pulp and 4 g of maleic anhydride (100 parts by mass relative to 100 parts by mass of dry pulp) were filled in an autoclave, and treated at 150° C. for 2 hours. Next, after washing the pulp treated with maleic anhydride three times with 500 mL of water, ion-exchanged water was added to prepare 490 mL of a maleic anhydride-treated pulp dispersion.

Next, while stirring the maleic anhydride-treated pulp dispersion, 10 mL of a 4N aqueous sodium hydroxide solution was gradually added in small amounts to adjust the pH to 12-13, thereby subjecting the pulp to alkali treatment. After that, the alkali-treated pulp was washed with water until the pH became 8 or less.

Next, ion-exchanged water was added to the alkali-treated pulp to prepare an alkali-treated pulp dispersion liquid having a solid content concentration of 0.5% by mass.

The resulting alkali-treated pulp dispersion was defibrated and centrifuged in the same manner as in Example 1-1, and the concentration was adjusted to obtain a supernatant (D).

(aggregation process · filtration process · redispersion process)

Using the supernatant (D), the steps of aggregation, filtration, and redispersion in Example 1-1 were carried out in the same manner to obtain a fine fibrous cellulose aqueous dispersion.

<Example 4-2>

Except not having added sodium hydroxide to the fine fibrous cellulose-containing liquid in the redispersion step, it carried out similarly to Example 4-1, and obtained the fine fibrous cellulose aqueous dispersion liquid.

<Example 4-3>

Except for omitting the aggregation step in Example 4-1 and concentrating the supernatant (D) instead of gel-like aggregates in the filtration step, it was carried out in the same manner as in Example 4-1 to obtain fine fibrous cellulose water Dispersions.

<Example 5-1>

In the same manner as in Example 1-1, except that the centrifugation of the fine fibrous cellulose dispersion in Example 1-1 was omitted and the fine fibrous cellulose dispersion was concentrated instead of the supernatant (A) in the concentration step implemented to obtain a fine fibrous cellulose aqueous dispersion.

<Example 5-2>

Except not having added sodium hydroxide to the fine fibrous cellulose-containing liquid in the redispersion step, it carried out similarly to Example 5-1, and obtained the fine fibrous cellulose aqueous dispersion liquid.

<Example 5-3>

Except for omitting the aggregation step in Example 5-1 and concentrating the fine fibrous cellulose dispersion instead of the gel-like aggregates in the concentration step, it was carried out in the same manner as in Example 5-1 to obtain fine fibrous cellulose water dispersion.

<Example 6-1>

In the same manner as in Example 3-1, except that the centrifugation of the fine fibrous cellulose dispersion in Example 3-1 was omitted and the fine fibrous cellulose dispersion was concentrated instead of the supernatant (C) in the concentration step implemented to obtain a fine fibrous cellulose aqueous dispersion.

<Example 6-2>

Except not having added sodium hydroxide to the fine fibrous cellulose-containing liquid in the redispersion step, it carried out similarly to Example 6-1, and obtained the fine fibrous cellulose aqueous dispersion liquid.

<Example 6-3>

Fine fibrous cellulose was obtained in the same manner as in Example 6-1, except that the aggregation step in Example 6-1 was omitted and the fine fibrous cellulose dispersion was concentrated in the concentration step instead of gel-like aggregates. water dispersion.

<Example 7-1> (chemical treatment process)

Using the same LBKP as that used in Example 1-1, beating was performed with a Niagara beater (capacity 23 liters, manufactured by Tozai Seiki Co., Ltd.) for 200 minutes to obtain a cellulose raw material dispersion (pulp concentration: 2% by mass). The obtained pulp slurry was dehydrated with a centrifugal dehydrator (manufactured by Kokusan Co., Ltd.) at 2000 rpm for 15 minutes to concentrate the pulp concentration to 25% by mass. Then, 60 parts by mass of the above-mentioned pulp, 7 parts by mass of sodium hydroxide, 2352 parts by mass of IPA, and 588 parts by mass of water were put into an IKA mixer whose rotation speed was adjusted to 800 rpm, and mixed at 30° C. After stirring for 30 minutes, the temperature was raised to 80° C., and 120 parts by mass of glycidyltrimethylammonium chloride was added as an active ingredient as a cationizing agent. After reacting for 1 hour, the reactant was taken out, neutralized, washed, and concentrated to obtain a cationized pulp with a density of 25% by mass.

(Defibration process)

Next, ion-exchanged water was added to the dispersion containing the cationized pulp to prepare an aqueous cellulose fiber dispersion having a cellulose fiber concentration of 0.5% by mass. Using a defibrating treatment device (manufactured by MTechnique Co., Ltd., Creamix-2.2S), under the condition of 21,500 rpm, the aforementioned cellulose fiber aqueous dispersion was subjected to a defibrating treatment for 30 minutes to obtain fine fibrous cellulose Dispersions.

The resulting fine fibrous cellulose dispersion was subjected to centrifugation at 12,000 G x 10 minutes (centrifuge: manufactured by Kokusan Co., Ltd., "H-200NR"), and the supernatant was recovered, and ions were added to the supernatant Water was exchanged to obtain a supernatant (E) having a cellulose content of 0.2% by mass.

(gathering process)

While stirring 110.5 g of the supernatant (E), 1N aqueous sodium hydroxide solution (inorganic base) was added to aggregate fine fibrous cellulose to obtain a gel-like aggregate at pH 12.

(filtering process)

A PTFE membrane filter (ADVANTEC company, pore size 0.5 μm) pre-soaked in isopropanol was placed on a Buchner funnel-type glass filter (manufactured by Advantech Co., Ltd., KG-90) with a sintered size of 30 μm to 50 μm, And set it on the filter bottle. The filtration area at this time was 0.00441 m ² .

Next, the obtained gel-like aggregates were placed on the aforementioned membrane filter at 23° C. under atmospheric pressure, and suction filtration was performed using an aspirator (suction pressure: 0.08 MPa) to concentrate the gel-like aggregates to obtain fine particles. Fibrous cellulose aggregates.

(redispersion process)

The fine fibrous cellulose aggregate obtained in the filtration step was added to water to obtain a fine fibrous cellulose-containing liquid. While stirring the fine fibrous cellulose-containing liquid, 4N hydrochloric acid was added to adjust the pH to 4.0. The total mass at this time was set to 110.5 g, which was the same as the supernatant (A) before the aggregation step. Thereafter, redispersion treatment was performed for 1 minute under the condition of 11,000 revolutions/minute using a homomixer (manufactured by IKA, ULTRA-TURRAX). Next, using an ultrasonic disperser (manufactured by Hielscher, UP400S), ultrasonic waves were irradiated for 30 seconds under the conditions of Cycle 1 and Amplitude 100%, thereby obtaining an aqueous dispersion of fine fibrous cellulose.

<Example 7-2>

Except not having added hydrochloric acid to the fine fibrous cellulose-containing liquid in the redispersion step, it carried out similarly to Example 7-1, and obtained the fine fibrous cellulose aqueous dispersion liquid.

<Example 7-3>

Except for omitting the aggregation step in Example 7-1 and concentrating the supernatant (E) instead of the gel-like aggregates in the filtration step, it was carried out in the same manner as in Example 7-1 to obtain fine fibrous cellulose water Dispersions.

<Embodiment 8>

12% by mass of the fine fibrous cellulose aggregates obtained in the filtration step in Example 1-1 were dried in an oven at 100°C to obtain 20% by mass of fine fibrous cellulose aggregates. Using this 20% by mass of fine fibrous cellulose aggregates, after performing pH adjustment in the same manner as in the redispersion step in Example 1, and using a homomixer, use an ultrasonic disperser (manufactured by Hielscher, UP400S) Under the conditions of Cycle 1 and Amplitude 100%, ultrasonic waves were irradiated for 30 seconds to obtain an aqueous dispersion of fine fibrous cellulose.

<Example 9>

12% by mass of the fine fibrous cellulose aggregates obtained in the filtration step in Example 1-1 were dried in an oven at 100°C to obtain 30% by mass of fine fibrous cellulose aggregates. Example 8 was carried out in the same manner to obtain a fine fibrous cellulose aqueous dispersion.

<Example 10>

12% by mass of the fine fibrous cellulose aggregates obtained in the filtration step in Example 1-1 were dried in an oven at 100°C to obtain 47% by mass of fine fibrous cellulose aggregates. Example 8 was carried out in the same manner to obtain a fine fibrous cellulose aqueous dispersion.

<Example 11>

12% by mass of the fine fibrous cellulose aggregates obtained in the filtration step in Example 1-1 were dried in an oven at 100°C to obtain 78% by mass of the fine fibrous cellulose aggregates. Example 8 was carried out in the same manner to obtain a fine fibrous cellulose aqueous dispersion.

<Example 12>

In the aggregation step of Example 1-1, instead of 4N sulfuric acid, a 2% by mass aluminum sulfate solution was added at 4% by mass relative to the dry mass of the pulp. The obtained fine fibrous cellulose aggregate was treated in the same manner as in the redispersion step of Example 8 to obtain a fine fibrous cellulose aqueous dispersion.

<Example 13>

In the _aggregation process, a polyaluminum chloride solution (manufactured by Asada Industry Co., Ltd., Paho# 2S) except having replaced 4N sulfuric acid, it carried out similarly to Example 12, and obtained the microfibrous cellulose aqueous dispersion liquid.

<Example 14>

In the aggregation process, a 10% by mass sodium sulfate solution, which is an aggregation agent containing polyvalent metal salts, is added at 200% by mass relative to the dry mass of the pulp instead of 1N sodium hydroxide. By performing the same procedure, an aqueous dispersion of fine fibrous cellulose was obtained.

<Example 15>

In the aggregation process, a 10% by mass disodium hydrogen phosphate solution, which is an aggregation agent containing a polyvalent metal salt, is added in place of 1N sodium hydroxide in an amount of 100% by mass relative to the dry mass of the pulp. -1 was carried out in the same manner to obtain a fine fibrous cellulose aqueous dispersion.

<Example 16>

In the aggregation process of Example 1-1, 10% by mass of didecyldimethylammonium chloride (manufactured by Daiichi Kogyo Pharmaceutical Co., Ltd., KachiogenDDM-PG ) to replace 4N sulfuric acid. The obtained fine fibrous cellulose aggregates were treated in the same manner as in the redispersion step of Example 8 to obtain a fine fibrous cellulose aqueous dispersion.

<Example 17>

In the aggregation step of Example 7-1, 10% by mass of 2% sodium oleate (anionic surfactant) was added to the dry mass of the pulp instead of the 1N aqueous sodium hydroxide solution. The obtained fine fibrous cellulose aggregates were treated in the same manner as in the redispersion step of Example 8 to obtain a fine fibrous cellulose aqueous dispersion.

<Example 18>

In the aggregation step of Example 9, in addition to 4N sulfuric acid, sorbitol (Sorbit T-70, manufactured by Mitsubishi Corporation Food Technology Co., Ltd.) which is a plasticizer was added in an amount of 5000% by mass relative to the dry mass of the pulp. The obtained fine fibrous cellulose aggregates were treated in the same manner as in the redispersion step of Example 8 to obtain a fine fibrous cellulose aqueous dispersion.

<Example 19>

In the aggregation step of Example 9, in addition to 4N sulfuric acid, ethylene glycol which is a plasticizer was added in an amount of 5000% by mass relative to the dry mass of the pulp. The obtained fine fibrous cellulose aggregates were treated in the same manner as in the redispersion step of Example 8 to obtain a fine fibrous cellulose aqueous dispersion.

<Example 20>

In the aggregation step of Example 9, in addition to 4N sulfuric acid, 5000% by mass of glycerin, which is a plasticizer, was added to the dry mass of the pulp. The obtained fine fibrous cellulose aggregates were treated in the same manner as in the redispersion step of Example 8 to obtain a fine fibrous cellulose aqueous dispersion.

(evaluate)

For the fine fibrous cellulose aggregates of each example, the average fiber width, fine fibrous cellulose content, liquid compound content, pH, filtration time during concentration, and redispersion of fine fibrous cellulose were measured by the following methods sex. The measurement results are shown in Tables 1-3.

[Average Fiber Width]

The average fiber width was measured by the method described in the section "(Fiber Width)" above.

[Fine fibrous cellulose content]

After measuring the mass of the fine fibrous cellulose aggregates, they were dried by heating at 105° C. for 12 hours to prepare a dried product, and the mass of the dried product was measured. Then, the fine fibrous cellulose content was determined by the formula [(mass of dried product)/(mass of fine fibrous cellulose aggregates)]×100.

[Liquid compound content]

By the formula [(mass of fine fibrous cellulose aggregates-mass of dry matter-added optional acid, alkali, mass of aggregating agent)/(mass of fine fibrous cellulose aggregates)] × 100, find Liquid compound content.

[pH]

Measurement was performed at 23°C using a pH meter.

[filter time]

The time taken to obtain fine fibrous cellulose aggregates from gel-like aggregates in the filtration step was measured. When the gloss on the surface of the fine fibrous cellulose aggregates disappeared and the mass of the filtrate reached 97% of the mass of the liquid at the start of the filtration, the measurement of the filtration time was terminated.

[Redispersibility]

For Examples 1 to 4 and 7 to 20, the haze of the supernatant before concentration (the supernatant before the aggregation process) and the haze after redispersion were measured using a haze meter HM-150 produced by Murakami Color Technology Research Institute Co., Ltd. Haze of an aqueous dispersion of fine fibrous cellulose.

For Examples 5 and 6, the haze and the haze and Haze of the aqueous dispersion of fine fibrous cellulose after redispersion.

The smaller the difference between the haze of the supernatant or the fine fibrous cellulose dispersion before concentration and the haze of the redispersed fine fibrous cellulose aqueous dispersion, the better the redispersibility.

[Table 1]

[Table 2]

[table 3]

In each example, an aqueous dispersion of fine fibrous cellulose was obtained by redispersing fine fibrous cellulose aggregates.

In addition, the examples (Examples 1-1, 1-2, 2-1, 2-2, 3-1, 3- 2, 4-1, 4-2, 5-1, 5-2, 6-1, 6-2, 7-1, 7-2, and 8-20), the filtration time is shorter, and the fine fibrous fibers Excellent redispersibility of pigment. In addition, in Examples 1-1, 2-1, 3-1, 4-1, 5-1, 6-1, and 8-13, 16, and 18-20 in which sodium hydroxide was added during redispersion, fine Fibrous cellulose is particularly excellent in redispersibility. In addition, in Examples 7-1, 14, 15, and 17 in which hydrochloric acid was added during redispersion, the redispersibility of fine fibrous cellulose was particularly excellent. In addition, in the case of Examples 18 to 20 in which a plasticizer for cellulose was contained in aggregates of fine fibrous cellulose, the redispersibility of fine fibrous cellulose was particularly excellent.

In the examples (Examples 1-3, 2-3, 3-3, 4-3, 5-3, 6-3, 7-3) in which the aggregation process was omitted to obtain fine fibrous cellulose aggregates, the filtration time lengthen.

Industrial availability

The present invention can provide a fine fibrous cellulose aggregate capable of reducing transportation costs and storage costs per unit of fine fibrous cellulose. In addition, a method for producing the fine fibrous cellulose aggregate for producing the fine fibrous cellulose aggregate can be provided.

Claims (17)

1. a microfibre shape cellulose aggregation, its liquefied compound containing microfibre shape cellulose that average fiber width is 2nm ~ 50nm and comprise at least one in water and organic solvent, the cellulosic content of described microfibre shape is 6 quality % ~ 80 quality % relative to the quality of microfibre shape cellulose aggregation entirety, and the content of described liquefied compound is more than 15 quality % relative to the quality of microfibre shape cellulose aggregation entirety.

2. microfibre shape cellulose aggregation according to claim 1, it is also containing the aggregating agent of salt comprising polyvalent metal.

3. microfibre shape cellulose aggregation according to claim 1 and 2, it is also containing at least one selected in the group of free acid, cationic surfactant and cationic macromolecule aggregation agent composition.

4. microfibre shape cellulose aggregation according to claim 1 and 2, it is also containing at least one in the group selecting free alkali, anionic surfactant and the agent of anionic property macromolecule aggregation to form.

5. the microfibre shape cellulose aggregation according to any one of claim 2 ~ 4, it is also containing cellulosic plasticizer.

6. the microfibre shape cellulose aggregation according to any one of Claims 1 to 5, wherein, more than the 40 quality % of the solid constituent comprised in described microfibre shape cellulose aggregation are described microfibre shape cellulose.

7. the microfibre shape cellulose aggregation according to any one of claim 1 ~ 6, wherein, the cellulosic maximum fiber width of described microfibre shape is below 50nm.

8. the manufacture method of a microfibre shape cellulose aggregation, it has the enrichment process of concentrated 1st microfibre shape cellulose dispersion liquid, and described 1st microfibre shape cellulose dispersion liquid contains the microfibre shape cellulose and the 1st decentralized medium that average fiber width is 2nm ~ 200nm.

9. the manufacture method of microfibre shape cellulose aggregation according to claim 8, wherein, described enrichment process has assembles operation and filter progress, described gathering operation is the operation that the described microfibre shape cellulose making to comprise in described 1st microfibre shape cellulose dispersion liquid is assembled, and described filter progress is described 1st microfibre shape cellulose dispersion liquid after filtering described gathering operation thus removes the operation of described 1st decentralized medium.

10. the manufacture method of microfibre shape cellulose aggregation according to claim 9, wherein, in described gathering operation, in described 1st microfibre shape cellulose dispersion liquid, add the aggregating agent of the salt containing polyvalent metal thus described microfibre shape cellulose is assembled.

The manufacture method of 11. microfibre shape cellulose aggregations according to claim 9 or 10, wherein, when the cellulosic surface charge of described microfibre shape is negative, in described gathering operation, in described 1st microfibre shape cellulose dispersion liquid, add at least one in the group selecting free acid, cationic surfactant and cationic macromolecule aggregation agent composition thus described microfibre shape cellulose is assembled.

The manufacture method of 12. microfibre shape cellulose aggregations according to claim 9 or 10, wherein, when the cellulosic surface charge of described microfibre shape is positive, in described gathering operation, in described 1st microfibre shape cellulose dispersion liquid, add at least one in the group selecting free alkali, anionic surfactant and the agent of anionic property macromolecule aggregation to form thus described microfibre shape cellulose is assembled.

13. microfibre shape cellulose aggregations according to any one of claim 9 ~ 12, wherein, described gathering operation comprises described microfibre shape cellulose aggregation and adds cellulosic plasticizer.

The manufacture method of the microfibre shape cellulose aggregation according to any one of 14. according to Claim 8 ~ 13, wherein, the microfibre shape content of cellulose of described 1st microfibre shape cellulose dispersion liquid is less than 6 quality % relative to the quality of microfibre shape cellulose aggregation entirety.

The manufacture method of 15. microfibre shape cellulose aggregations according to claim 14, wherein, in described enrichment process, carry out concentrated to make the cellulosic content of described microfibre shape be 6 quality % ~ 80 quality % relative to the quality of microfibre shape cellulose aggregation entirety.

The reproducing method of 16. 1 kinds of microfibre shape cellulose dispersion liquids, it has dispersion step again, the 2nd decentralized medium is added in the described microfibre shape cellulose aggregation that described dispersion step again obtains in the manufacture method by the microfibre shape cellulose aggregation according to any one of claim 8 ~ 15, thus preparation the 2nd microfibre shape cellulose contains liquid, and liquid enforcement dispersion treatment is contained to described 2nd microfibre shape cellulose.

The reproducing method of 17. microfibre shape cellulose dispersion liquids according to claim 16, wherein, in described dispersion step again, when the cellulosic surface charge of described microfibre shape is negative, described 2nd microfibre shape cellulose is contained liquid and is adjusted to more than pH7 and below pH12, when the cellulosic surface charge of described microfibre shape is positive, described 2nd microfibre shape cellulose is contained liquid and is adjusted in the scope of pH4 ~ pH7.